CN102139880B - Method for removing impurity boron in polycrystalline silicon by electron beam slagging smelting - Google Patents

Method for removing impurity boron in polycrystalline silicon by electron beam slagging smelting Download PDF

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CN102139880B
CN102139880B CN2011101259039A CN201110125903A CN102139880B CN 102139880 B CN102139880 B CN 102139880B CN 2011101259039 A CN2011101259039 A CN 2011101259039A CN 201110125903 A CN201110125903 A CN 201110125903A CN 102139880 B CN102139880 B CN 102139880B
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electron beam
boron
polycrystalline silicon
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smelting
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CN102139880A (en
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谭毅
战丽姝
邹瑞洵
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Dalian Longsheng Technology Co., Ltd.
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Qingdao Longsheng Crystal Silicon Technology Co Ltd
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Abstract

The invention belongs to the technical field of polycrystalline silicon purification by using a physical metallurgy technique and relates to a method for removing impurity boron in polycrystalline silicon by electron beam slagging smelting. The method comprises the following steps: evenly mixing a cleaned polycrystalline silicon material with a slagging flux so as to form a mixed material; carrying out pretreatment: putting the mixed material into a smelting crucible in an electron beam smelting furnace, carrying out crucible water cooling on the smelting crucible, and preheating an electronic gun; bombarding the mixed material by using a small-beam electron beam so as smelt the mixed material, then increasing the electron beam to 250-500 mA for smelting; and reacting the impurity boron with the base slagging flux so as to generate gas which is volatilized and removed, cooling and solidifying to obtain a polycrystalline silicon ingot with low boron. In the method, an electron beam slagging smelting technique is used and the characteristics of removing boron by slagging and removing volatile impurity by the electron beam are combined; the process is simpler, and the electron beam and the slagging process are effectively combined; the method has the advantages of mild process conditions, short production period, good purification effect, stable technique and high production efficiency, and is easy to operate; and energy is saved, and consumption is reduced.

Description

The method of impurity boron out of polysilicon is removed in a kind of electron beam slag making melting
Technical field
The invention belongs to technical field, particularly a kind of method of utilizing electron beam to remove impurity boron out of polysilicon with physical metallurgy technology purifying polycrystalline silicon.
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.Solar cell can be an electric energy with solar energy converting, solar grade polycrystalline silicon material is to make the most important basic raw material of solar cell, but manufacturing cost that it is high and complicated manufacturing process are the bottlenecks of restriction photovoltaic industry great development, have seriously hindered the popularization and the use of China's solar cell.
At present, in the world wide there be the main technological route of preparation solar grade polycrystalline silicon material: improvement Siemens Method, silane thermal decomposition process, metallurgy method.Wherein improve siemens's ratio juris and be exactly on the HIGH-PURITY SILICON core about 1100 ℃ with High Purity Hydrogen and reduce high-purity trichlorosilane, generate polysilicon deposition on the silicon core.But improvement Siemens Method energy consumption height, seriously polluted belongs to American-European old technology of eliminating.Silane thermal decomposition process is exactly silane (SiH 4) thermolysis prepares the method for polysilicon, but dangerous big (silane is inflammable and explosive) during this explained hereafter operation, comprehensive production cost are higher.Metallurgy method mainly comprises: electron-beam process, beam-plasma smelting process, directional solidification method, slag practice, electrolytic process, carbothermic method etc.
Comparatively speaking metallurgy method has characteristics with short production cycle, that pollution is little, cost is low, is the emphasis that various countries competitively research and develop.The electron beam melting technology is that metallurgy method prepares one of important method in the solar level, it is to utilize the processing method of the electron beam of high-energy-density as the melting thermal source, it is applied in the metallurgical melting, be used to melt the purification material, known application number is the preparation method's of a kind of solar energy level silicon of 200810068908.0 a patent of invention, utilize the directional solidification furnace of induction heating to carry out the slag making melting except that boron, but complex process in this method, production cycle is longer, cost is higher, and impurity removal efficacy is not high.
Summary of the invention
The objective of the invention is to overcome above-mentioned not enough problem, provide a kind of electron beam slag making melting to remove the method for impurity boron out of polysilicon, combine slagging boron removal and electron beam is removed volatile impunty, boron impurities in the polysilicon is removed to degree below 0.0001%, thereby reaches the service requirements of silicon material for solar cells.
The technical solution used in the present invention is: the method for impurity boron out of polysilicon is removed in a kind of electron beam slag making melting, and at first get the raw materials ready: polycrystalline silicon material and slag former after will cleaning are uniformly mixed to form compound; Pre-treatment again: compound is put into the smelting pot of electron beam melting furnace, smelting pot is carried out water-cooled, pre-thermionic electron guns; Purify at last: adopt tuftlet stream beam bombardment compound, compound fusing back increases electron beam and carries out melting to 250-500mA, boron impurities generates gaseous volatilization with alkaline slag former reaction and removes in fusion process, cooled and solidified obtains the polycrystal silicon ingot of low boron.
Described getting the raw materials ready: at first get high boron polycrystalline silicon material, use washed with de-ionized water 4-5 time, put into 60 ℃ of oven dry of drying baker, the high boron polycrystalline silicon material and the alkaline slag former of drying is uniformly mixed to form compound in proportion;
Described pre-treatment: the electron beam melting furnace vacuum is evacuated to below the 0.002Pa with the vacuum pump group; Bottom band refrigerative smelting pot is carried out water-cooled, and temperature maintenance is at 25-45 ℃; Pre-thermionic electron guns, it is 28-30kV that high pressure is set, and the high pressure preheating was closed high pressure after 5-10 minute, and the electron beam gun line is set to 100-200mA, carries out preheating, after preheating 10-15 minute, closes the electron beam gun line.
Described purification: high pressure and the line of opening electron beam gun, stable back is bombarded compound with electron beam gun with the 150-300mA line, material to be mixed melts the line of back increase electron beam fully to 250-500mA, melting 10-30min under this line, under the high temperature in the molten bath reaction of boron impurities and oxidisability alkalescence slag former generate gas and the removal of volatilizing, reducing line is zero, and the molten bath cooled and solidified forms the polycrystal silicon ingot that hangs down boron.
Described alkaline slag former is SiO 2-CaO-CaF 2, wherein the shared mass percent of each component is SiO 220-40%, CaO40-60% and CaF 210-30%.
The mass ratio of described compound neutral and alkali slag former and polycrystalline silicon material is 0.1-0.8.
Described high boron polycrystalline silicon material is piece material or powder.
Unusual effect of the present invention is to have adopted document that the technology of any disclosed electron beam slag making melting is not arranged, combine slagging boron removal and electron beam and remove the characteristics of volatile impunty, utilize strong alkaline slag former of oxidisability and high boron polycrystalline silicon material to form compound, then under the high temperature that electron beam produces, melt, oxygen reaction in boron impurities and the slag former produces the stronger gaseous substance of volatility, finally being evacuated device takes away, thereby realize removing the purpose of boron impurity, to satisfy the service requirements of solar energy level silicon.This method is compared with the directional freeze slag making melting method of induction heating, and technology is simpler, effectively electron beam is combined with slagging process, and the gentle easy handling of processing condition, with short production cycle, energy-saving and cost-reducing, refining effect is good, and is consistent, the production efficiency height.
Description of drawings
Accompanying drawing 1 is removed the schema of the method for impurity boron out of polysilicon for a kind of electron beam slag making of the present invention melting.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiments and the drawings 1, but the present invention is not limited to specific embodiment.
Embodiment 1
The first step is got the raw materials ready: at first getting 500g boron content is 0.0013% polysilicon block material, uses washed with de-ionized water 4 times, puts into 60 ℃ of oven dry of drying baker, with the high boron polycrystalline silicon material and the 50g SiO of oven dry 2-CaO-CaF 2Oxidisability alkalescence slag former is uniformly mixed to form compound in the 10:1 ratio, wherein SiO 2, CaO and CaF 2Mass percent be respectively 20%, 50% and 30%.
The second step pre-treatment: the electron beam melting furnace vacuum is evacuated to 0.0018Pa with the vacuum pump group; Bottom band refrigerative smelting pot is carried out water-cooled, and temperature maintenance is at 40 ℃; Pre-thermionic electron guns, it is 30kV that high pressure is set, and the high pressure preheating was closed high pressure after 5 minutes, and the electron beam gun line is set to 200mA, carries out preheating, and preheating was closed the electron beam gun line after 10 minutes;
The 3rd step purified: high pressure and the line of opening electron beam gun, stable back is bombarded compound with electron beam gun with the 150mA line, material to be mixed melts the line of back increase electron beam fully to 250mA, melting 20min under this line, under the high temperature in the molten bath reaction of the oxidisability slag agent in boron impurities and the impurity generate gas and the removal of volatilizing, fall little line at last and be zero, the molten bath cooled and solidified obtains boron content and is 0.00009% polycrystal silicon ingot.
Embodiment 2
The first step is got the raw materials ready: at first getting 600g boron content is 0.001% polysilicon block material, uses washed with de-ionized water 4 times, puts into 60 ℃ of oven dry of drying baker, with the high boron polycrystalline silicon material and the 120g SiO of oven dry 2-CaO-CaF 2Oxidisability alkalescence slag former is uniformly mixed to form compound in the 5:1 ratio, wherein SiO 2, CaO and CaF 2Mass percent be respectively 25%, 60% and 15%.
The second step pre-treatment: the electron beam melting furnace vacuum is evacuated to 0.0016Pa with the vacuum pump group; Bottom band refrigerative smelting pot is carried out water-cooled, and temperature maintenance is at 35 ℃; Pre-thermionic electron guns, it is 30kV that high pressure is set, and the high pressure preheating was closed high pressure after 5 minutes, and the electron beam gun line is set to 100mA, carries out preheating, and preheating was closed the electron beam gun line after 15 minutes;
The 3rd step purified: high pressure and the line of opening electron beam gun, stable back is bombarded compound with electron beam gun with the 300mA line, material to be mixed melts the line of back increase electron beam fully to 500mA, melting 20min under this line, under the high temperature in the molten bath reaction of the oxidisability slag agent in boron impurities and the impurity generate gas and the removal of volatilizing, fall little line at last and be zero, the molten bath cooled and solidified obtains boron content and is 0.00008% polycrystal silicon ingot.
Embodiment 3
The first step is got the raw materials ready: at first getting 500g boron content is 0.001% polysilicon block material, uses washed with de-ionized water 4 times, puts into 60 ℃ of oven dry of drying baker, with the high boron polycrystalline silicon material and the 350g SiO of oven dry 2-CaO-CaF 2Oxidisability alkalescence slag former is uniformly mixed to form compound in the 10:7 ratio, wherein SiO 2, CaO and CaF 2Mass percent be respectively 40%, 50% and 10%.
The second step pre-treatment: the electron beam melting furnace vacuum is evacuated to 0.0016Pa with the vacuum pump group; Bottom band refrigerative smelting pot is carried out water-cooled, and temperature maintenance is at 35 ℃; Pre-thermionic electron guns, it is 28kV that high pressure is set, and the high pressure preheating was closed high pressure after 6 minutes, and the electron beam gun line is set to 150mA, carries out preheating, and preheating was closed the electron beam gun line after 15 minutes;
The 3rd step purified: high pressure and the line of opening electron beam gun, stable back is bombarded compound with electron beam gun with the 200mA line, material to be mixed melts the line of back increase electron beam fully to 300mA, melting 30min under this line, under the high temperature in the molten bath reaction of the oxidisability slag agent in boron impurities and the impurity generate gas and the removal of volatilizing, fall little line at last and be zero, the molten bath cooled and solidified obtains boron content and is 0.00008% polycrystal silicon ingot.
Embodiment 4
The first step is got the raw materials ready: at first getting 500g boron content is 0.001% polysilicon block material, uses washed with de-ionized water 4 times, puts into 60 ℃ of oven dry of drying baker, with the high boron polycrystalline silicon material and the 250g SiO of oven dry 2-CaO-CaF 2Oxidisability alkalescence slag former is uniformly mixed to form compound in the 2:1 ratio, wherein SiO 2, CaO and CaF 2Mass percent be respectively 30%, 45% and 25%.
The second step pre-treatment: the electron beam melting furnace vacuum is evacuated to 0.0016Pa with the vacuum pump group; Bottom band refrigerative smelting pot is carried out water-cooled, and temperature maintenance is at 35 ℃; Pre-thermionic electron guns, it is 30kV that high pressure is set, and the high pressure preheating was closed high pressure after 7 minutes, and the electron beam gun line is set to 100mA, carries out preheating, and preheating was closed the electron beam gun line after 15 minutes;
The 3rd step purified: high pressure and the line of opening electron beam gun, stable back is bombarded compound with electron beam gun with the 250mA line, material to be mixed melts the line of back increase electron beam fully to 400mA, melting 30min under this line, under the high temperature in the molten bath reaction of the oxidisability slag agent in boron impurities and the impurity generate gas and the removal of volatilizing, fall little line at last and be zero, the molten bath cooled and solidified obtains boron content and is 0.00008% polycrystal silicon ingot.
The present invention is good through the case test refining effect except that boron, and technology is simple, and is with short production cycle, and energy consumption is little, and cost is low, and production efficiency is higher, is fit to produce in batches.

Claims (5)

1. the method for impurity boron out of polysilicon is removed in an electron beam slag making melting, and it is characterized in that: at first get the raw materials ready: polycrystalline silicon material and slag former after will cleaning are uniformly mixed to form compound; Pre-treatment again: compound is put into the smelting pot of electron beam melting furnace, smelting pot is carried out the crucible water-cooled, pre-thermionic electron guns; Purify at last: high pressure and the line of opening electron beam gun, stable back is bombarded compound with electron beam gun with the 150-300mA line, material to be mixed melts the line of back increase electron beam fully to 250-500mA, melting 10-30min under this line, under the high temperature in the molten bath reaction of boron impurities and oxidisability alkalescence slag former generate gas and the removal of volatilizing, reducing line is zero, and the molten bath cooled and solidified forms the polycrystal silicon ingot that hangs down boron; Wherein said alkaline slag former is SiO 2-CaO-CaF 2, wherein the shared mass percent of each component is SiO 220-40%, CaO40-60% and CaF 225-30%.
2. the method for impurity boron out of polysilicon is removed in a kind of electron beam slag making melting according to claim 1, it is characterized in that: described getting the raw materials ready: at first get high boron polycrystalline silicon material, with washed with de-ionized water 4-5 time, put into 60 ℃ of oven dry of drying baker, the high boron polycrystalline silicon material and the alkaline slag former of drying is uniformly mixed to form compound in proportion.
3. the method for impurity boron out of polysilicon is removed in a kind of electron beam slag making melting according to claim 1, it is characterized in that: described pre-treatment: with the vacuum pump group electron beam melting furnace vacuum is evacuated to below the 0.002Pa; Bottom band refrigerative smelting pot is carried out water-cooled, and temperature maintenance is at 25-45 ℃; Pre-thermionic electron guns, it is 28-30kV that high pressure is set, and the high pressure preheating was closed high pressure after 5-10 minute, and the electron beam gun line is set to 100-200mA, carries out preheating, after preheating 10-15 minute, closes the electron beam gun line.
4. according to the method for the arbitrary described a kind of electron beam slag making melting removal impurity boron out of polysilicon of claim 1-3, it is characterized in that: the mass ratio of described compound neutral and alkali slag former and polycrystalline silicon material is 0.1-0.8.
5. according to the method for the arbitrary described a kind of electron beam slag making melting removal impurity boron out of polysilicon of claim 1-3, it is characterized in that: described high boron polycrystalline silicon material is piece material or powder.
CN2011101259039A 2011-05-16 2011-05-16 Method for removing impurity boron in polycrystalline silicon by electron beam slagging smelting Expired - Fee Related CN102139880B (en)

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CN101724900A (en) * 2009-11-24 2010-06-09 厦门大学 Device and method for purifying polycrystalline silicon
CN101941698A (en) * 2010-08-17 2011-01-12 大连隆田科技有限公司 Method and device for efficiently removing phosphorus impurities in silicon by electron beam melting

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101724900A (en) * 2009-11-24 2010-06-09 厦门大学 Device and method for purifying polycrystalline silicon
CN101941698A (en) * 2010-08-17 2011-01-12 大连隆田科技有限公司 Method and device for efficiently removing phosphorus impurities in silicon by electron beam melting

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