CN104556050B - A kind of electron beam is crossed hot smelting and is removed the method and apparatus of metal impurities in polysilicon - Google Patents
A kind of electron beam is crossed hot smelting and is removed the method and apparatus of metal impurities in polysilicon Download PDFInfo
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- CN104556050B CN104556050B CN201410829665.3A CN201410829665A CN104556050B CN 104556050 B CN104556050 B CN 104556050B CN 201410829665 A CN201410829665 A CN 201410829665A CN 104556050 B CN104556050 B CN 104556050B
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- graphite bushing
- copper crucible
- jacketed copper
- water jacketed
- electron gun
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Abstract
The invention discloses a kind of electron beam and cross the method and apparatus of metal impurities in hot smelting removal polysilicon, belong to field of metallurgy.Described device includes water-cooled melting kettle, described water jacketed copper crucible uses tilting sidewall design, angle at the bottom of described water jacketed copper crucible medial wall and water jacketed copper crucible is 105～120 °, it is provided with graphite bushing in described water jacketed copper crucible, described graphite bushing outer surface is fitted with water jacketed copper crucible inner surface, tight fit designs, the bottom of graphite bushing and water jacketed copper crucible bottom level, and angle at the bottom of described graphite bushing inner surface sidewall and graphite bushing is 95～100 °.In apparatus of the present invention, carry out hot smelting removed metal impurities, the number of times of follow-up directional solidification and ingot casting can be reduced, reduced purifying technique, reduce production cost；Polycrystalline silicon purifying electron beam crosses hot smelting can reduce later stage directional solidification number of times more than 1 time；Polycrystalline silicon purifying electron beam crosses hot smelting can reduce metal impurities more than 30% in polysilicon.
Description
Technical field
The present invention relates to a kind of electron beam and cross the method for metal impurities in hot smelting removal polysilicon, belong to field of metallurgy.
Background technology
Metallurgy method prepares solar-grade polysilicon, due to the features such as its low cost, little, the environmental friendliness of energy consumption, quilt at present
Promote widely and use.In the technique purified, according to impurity existence form in polysilicon and each impurity unit
The physicochemical properties of element, mainly utilize the method for slag making melting to remove the boron impurity in polysilicon, utilize directional solidification
The method that the method for (ingot casting) or pickling is removed the metal impurities in polysilicon, utilized electronic torch melting or vacuum melting
Remove the phosphorus impurities in polysilicon.
Currently for the metal impurities total concentration polysilicon more than 1000ppmw, need through twice even twice with
On directional solidification technique metal impurities total concentration could be reduced to below 1ppmw.And at directional solidification technique proposition
The reason time once, the production time was longer about 1～2 day time, and wasted big during repeatedly purifying
The electric power of amount.
Summary of the invention
In order to solve the problems referred to above, the present invention provides a kind of overheated melting technique of electron beam, makes polysilicon melt at electron beam
Just a directional solidification be can carry out the when of refining, difficulty and the cost of subsequent treatment lowered.
It is an object of the invention to provide the device of a kind of electronic torch melting polysilicon, including water-cooled melting kettle, described water
Cold copper crucible uses the angle at the bottom of tilting sidewall design, described water jacketed copper crucible medial wall and water jacketed copper crucible to be
105～120 °, in described water jacketed copper crucible, it is provided with graphite bushing, described graphite bushing outer surface and table in water jacketed copper crucible
Fitting in face, tight fit designs, the bottom of graphite bushing and water jacketed copper crucible bottom level, described graphite bushing inner surface
Angle at the bottom of sidewall and graphite bushing is 95～100 °.
Further, in technique scheme, described graphite bushing bottom thickness is 20～40mm, and described graphite serves as a contrast
Bottom the side thickness at the end, degree is more than or equal to 20mm.
Ratio further, in technique scheme, between internal height and the bottom width of described graphite bushing
For 1:1～2:1.
It is a further object of the present invention to provide a kind of electron beam and cross the method for metal impurities in hot smelting removal polysilicon, its
It is characterised by comprising the following steps:
A. water jacketed copper crucible is placed in the lower section of electron gun, graphite bushing is placed in water jacketed copper crucible, will be broken into
The silicon material of 10～30mm loads in graphite bushing, and described silicon material is filled the feeding device of electronic torch melting simultaneously；
The most pre-thermionic electron guns；
C. fusing, melting silicon material；Open high pressure and the line of electron gun simultaneously, gradually promote the monitor system of electron gun
To 200～300kW, power ascension speed is 5～10kW/min；After melted silicon material, continue melting 20-40min；By
Heat conductivity in graphite material is far smaller than the heat conductivity of copper material, so graphite bushing has insulation effect, meeting
Make the superheat state that the silicon melt under electronic torch melting reaches 2000～2600 DEG C, the volatile impurity of silicon melt surface
Removal rate is accelerated.Simultaneously as the not uniform thickness design of graphite bushing sidewall, make the temperature of silicon melt from bottom to top in
The thermograde now gradually risen, forms directional solidification trend, makes metal impurities gradually migrate to silicon melt surface or fortune
Dynamic, the volatile impurity reaching silicon melt surface is removed；
D. electron gun is closed, the silicon material furnace cooling 1～3h after melting, close diffusion pump, lobe pump, mechanical pump successively,
Open vent valve, open equipment door and take out silicon ingot；
E. the impurity of non-volatility can concentrate on the upper surface of silicon ingot due to directional solidification effect, and upper surface excises
5～10mm.
Further, in upper art technical scheme, in step b, close equipment door, open mechanical pump, sieve successively
Thatch pump, diffusion pump, make the vacuum of working chamber reach 5 × 10-2Pa, the vacuum of electron gun reaches 5 × 10-3Pa；
It is 25-35kW that electron gun arranges high pressure, after high pressure preheating 5-10min, closes high pressure, and arranging electron gun line is
70-200mA, line preheating 5-10min, close electron gun line.
Further, in technique scheme, in step c, along with the carrying out of melting, by feeding device to graphite
Lining adds silicon material, repeats step c, until reaching specified amount.
The present invention is by adding graphite bushing in electron-beam melting system in water jacketed copper crucible, it is overheated to carry out silicon melt
Melting, makes silicon melt dispel the heat not in time, under the effect of thermograde, forms orientation from bottom to top solidifying inside silicon melt
Gu trend, metal impurities are enriched to top, and volatile impurity escapes from silicon melt top, non-volatile impurities final set
It is fixed in the top of silicon ingot, the most cut.
Invention beneficial effect
In apparatus of the present invention, carried out hot smelting removed metal impurities, follow-up directional solidification and ingot casting can be reduced
Number of times, reduces purifying technique, reduces production cost；Polycrystalline silicon purifying electron beam crosses hot smelting, and can to reduce later stage orientation solidifying
Gu number of times more than 1 time；Polycrystalline silicon purifying electron beam crosses hot smelting can reduce metal impurities more than 30% in polysilicon.
Accompanying drawing explanation
Accompanying drawing 1 width of the present invention,
Fig. 1 is apparatus of the present invention structural representations；
In figure, 1, water jacketed copper crucible；2, graphite muff.
Detailed description of the invention
Following nonlimiting examples can make those of ordinary skill in the art that the present invention be more fully understood, but not with
Any mode limits the present invention.
Test method described in following embodiment, if no special instructions, is conventional method；Described reagent and material,
If no special instructions, the most commercially obtain.
Embodiment 1
As it is shown in figure 1, the device of a kind of electronic torch melting polysilicon, including water-cooled melting kettle, described water-cooled copper earthenware
Angle at the bottom of crucible medial wall and water jacketed copper crucible is 105 °, is provided with graphite bushing, described graphite in described water jacketed copper crucible
Sleeve outer surface is fitted with water jacketed copper crucible inner surface, the bottom of graphite bushing and water jacketed copper crucible bottom level, described
Angle at the bottom of graphite bushing inner surface sidewall and graphite bushing is 95 °.
Described graphite bushing bottom thickness is 20mm.
The sidewall thinnest part thickness of described graphite substrate is equal to 20mm.
Ratio between internal height H and the bottom width W of described graphite bushing is 1:1.
A kind of electron beam is crossed hot smelting and is removed the method for metal impurities in polysilicon, comprises the following steps:
A. water jacketed copper crucible is placed in the lower section of electron gun, graphite bushing is placed in water jacketed copper crucible, will be broken into
The silicon material of 10～30mm loads in graphite bushing, and described silicon material is filled the feeding device of electronic torch melting simultaneously；
The most pre-thermionic electron guns；Closedown equipment door, opens mechanical pump, lobe pump, diffusion pump successively, makes working chamber
Vacuum reaches 5 × 10-2Pa, the vacuum of electron gun reaches 5 × 10-3Pa；It is 25kW that electron gun arranges high pressure, high
After pressure preheating 10min, closing high pressure, arranging electron gun line is 70mA, line preheating 10min, closes electronics
Rifle line；
C. fusing, melting silicon material；Open high pressure and the line of electron gun simultaneously, gradually promote the monitor system of electron gun
To 200kW, power ascension speed is 5kW/min；After melted silicon material, continue melting 40min；Due to graphite material
Heat conductivity be far smaller than the heat conductivity of copper material, so graphite bushing has insulation effect, electron beam can be made to melt
Silicon melt under Lian reaches the superheat state of 2000 DEG C, and the removal rate of the volatile impurity of silicon melt surface is accelerated.With
Time, owing to the not uniform thickness of graphite bushing sidewall designs, make the temperature of silicon melt present the temperature gradually risen from bottom to top
Gradient, forms directional solidification trend, makes metal impurities gradually migrate to silicon melt surface or motion, reaches silicon melt table
The volatile impurity in face is removed；
D. along with the carrying out of melting, feeding device in graphite bushing, add silicon material, repeat step c, until reaching
Specified amount；
E. electron gun is closed, the silicon material furnace cooling 1h after melting, close diffusion pump, lobe pump, mechanical pump successively,
Open vent valve, open equipment door and take out silicon ingot；
F. the impurity of non-volatility can concentrate on the upper surface of silicon ingot, upper surface excision 10mm due to directional solidification effect.
Embodiment 2
As it is shown in figure 1, the device of a kind of electronic torch melting polysilicon, including water-cooled melting kettle, described water-cooled copper earthenware
Angle at the bottom of crucible medial wall and water jacketed copper crucible is 110 °, is provided with graphite bushing, described graphite in described water jacketed copper crucible
Sleeve outer surface is fitted with water jacketed copper crucible inner surface, the bottom of graphite bushing and water jacketed copper crucible bottom level, described
Angle at the bottom of graphite bushing inner surface sidewall and graphite bushing is 97 °.
Described graphite bushing bottom thickness is 30mm.
The sidewall thinnest part thickness of described graphite substrate is equal to 20mm.
Ratio between internal height H and the bottom width W of described graphite bushing is 1.5:1.
A kind of electron beam is crossed hot smelting and is removed the method for metal impurities in polysilicon, comprises the following steps:
A. water jacketed copper crucible is placed in the lower section of electron gun, graphite bushing is placed in water jacketed copper crucible, will be broken into
The silicon material of 10～30mm loads in graphite bushing, and described silicon material is filled the feeding device of electronic torch melting simultaneously；
The most pre-thermionic electron guns；Closedown equipment door, opens mechanical pump, lobe pump, diffusion pump successively, makes working chamber
Vacuum reaches 5 × 10-2Pa, the vacuum of electron gun reaches 5 × 10-3Pa；It is 30kW that electron gun arranges high pressure, high
After pressure preheating 8min, closing high pressure, arranging electron gun line is 135mA, line preheating 8min, closes electron gun
Line；
C. fusing, melting silicon material；Open high pressure and the line of electron gun simultaneously, gradually promote the monitor system of electron gun
To 250kW, power ascension speed is 7.5kW/min；After melted silicon material, continue melting 20min；Due to graphite material
The heat conductivity of matter is far smaller than the heat conductivity of copper material, so graphite bushing has insulation effect, can make electron beam
Silicon melt under melting reaches the superheat state of 2300 DEG C, and the removal rate of the volatile impurity of silicon melt surface is accelerated.
Simultaneously as the not uniform thickness design of graphite bushing sidewall, the temperature of silicon melt is made to present the temperature gradually risen from bottom to top
Degree gradient, forms directional solidification trend, makes metal impurities gradually migrate to silicon melt surface or motion, reaches silicon melt
The volatile impurity on surface is removed；
D. along with the carrying out of melting, feeding device in graphite bushing, add silicon material, repeat step c, until reaching
Specified amount；
E. electron gun is closed, the silicon material furnace cooling 2h after melting, close diffusion pump, lobe pump, mechanical pump successively,
Open vent valve, open equipment door and take out silicon ingot；
F. the impurity of non-volatility can concentrate on the upper surface of silicon ingot, upper surface excision 8mm due to directional solidification effect.
Embodiment 3
As it is shown in figure 1, the device of a kind of electronic torch melting polysilicon, including water-cooled melting kettle, described water-cooled copper earthenware
Angle at the bottom of crucible medial wall and water jacketed copper crucible is 120 °, is provided with graphite bushing, described graphite in described water jacketed copper crucible
Sleeve outer surface is fitted with water jacketed copper crucible inner surface, the bottom of graphite bushing and water jacketed copper crucible bottom level, described
Angle at the bottom of graphite bushing inner surface sidewall and graphite bushing is 100 °.
Described graphite bushing bottom thickness is 40mm.
The sidewall thinnest part thickness of described graphite substrate is equal to 20mm.
Ratio between internal height H and the bottom width W of described graphite bushing is 2:1.
A kind of electron beam is crossed hot smelting and is removed the method for metal impurities in polysilicon, comprises the following steps:
A. water jacketed copper crucible is placed in the lower section of electron gun, graphite bushing is placed in water jacketed copper crucible, will be broken into
The silicon material of 10～30mm loads in graphite bushing, and described silicon material is filled the feeding device of electronic torch melting simultaneously；
The most pre-thermionic electron guns；Closedown equipment door, opens mechanical pump, lobe pump, diffusion pump successively, makes working chamber
Vacuum reaches 5 × 10-2Pa, the vacuum of electron gun reaches 5 × 10-3Pa；It is 35kW that electron gun arranges high pressure, high
After pressure preheating 5min, closing high pressure, arranging electron gun line is 200mA, line preheating 5min, closes electron gun
Line；
C. fusing, melting silicon material；Open high pressure and the line of electron gun simultaneously, gradually promote the monitor system of electron gun
To 300kW, power ascension speed is 10kW/min；After melted silicon material, continue melting 20-40min；Due to graphite
The heat conductivity of material is far smaller than the heat conductivity of copper material, so graphite bushing has insulation effect, can make electronics
Silicon melt under bundle melting reaches the superheat state of 2600 DEG C, and the removal rate of the volatile impurity of silicon melt surface adds
Hurry up.Simultaneously as the not uniform thickness design of graphite bushing sidewall, make the temperature of silicon melt present from bottom to top and gradually rise
Thermograde, formed directional solidification trend, make metal impurities gradually to silicon melt surface migrate or motion, reach silicon
The volatile impurity of bath surface is removed；
D. along with the carrying out of melting, feeding device in graphite bushing, add silicon material, repeat step c, until reaching
Specified amount；
E. electron gun is closed, the silicon material furnace cooling 3h after melting, close diffusion pump, lobe pump, mechanical pump successively,
Open vent valve, open equipment door and take out silicon ingot；
F. the impurity of non-volatility can concentrate on the upper surface of silicon ingot, upper surface excision 5mm due to directional solidification effect.
Claims (6)
1. an electron beam is crossed hot smelting and is removed the device of metal impurities in polysilicon, including water-cooled melting kettle, it is characterized in that: angle at the bottom of described water jacketed copper crucible medial wall and water jacketed copper crucible is 105～120 °, it is provided with graphite bushing in described water jacketed copper crucible, described graphite bushing outer surface is fitted with water jacketed copper crucible inner surface, angle at the bottom of the bottom of graphite bushing and water jacketed copper crucible bottom level, described graphite bushing inner surface sidewall and graphite bushing is 95～100 °.
Device the most according to claim 1, it is characterised in that: described graphite bushing bottom thickness is 20～40mm；The sidewall bottom thickness of described graphite substrate is more than or equal to 20mm.
Device the most according to claim 1 and 2, it is characterised in that: the ratio between internal height and the bottom width of described graphite bushing is 1:1～2:1.
4. one kind utilizes device described in any one of claim 1～3 to carry out electron beam to cross hot smelting and remove the method for metal impurities in polysilicon, it is characterised in that comprise the following steps:
A. water jacketed copper crucible is placed in the lower section of electron gun, graphite bushing is placed in water jacketed copper crucible, the silicon material being broken into 10～30mm is loaded in graphite bushing, described silicon material is filled the feeding device of electronic torch melting simultaneously；
The most pre-thermionic electron guns；
C. fusing, melting silicon material；Opening high pressure and the line of electron gun simultaneously, gradually promote the monitor system of electron gun to 200～300kW, power ascension speed is 5～10kW/min, after melted silicon material, continues melting 20-40min；
D. electron gun is closed, the silicon material furnace cooling 1～3h after melting, close diffusion pump, lobe pump, mechanical pump successively, open vent valve, open equipment door and take out silicon ingot；
E. the impurity of non-volatility can concentrate on the upper surface of silicon ingot due to directional solidification effect, excises silicon ingot upper surface 5～10mm.
Method the most according to claim 4, it is characterised in that: in step b, close equipment door, open mechanical pump, lobe pump, diffusion pump successively, make the vacuum of working chamber reach 5 × 10-2Pa, the vacuum of electron gun reaches 5 × 10-3Pa；It is 25-35kW that electron gun arranges high pressure, after high pressure preheating 5-10min, closes high pressure, and arranging electron gun line is 70-200mA, and line preheating 5-10min closes electron gun line.
Method the most according to claim 4, it is characterised in that: in step c, after melting, in graphite bushing, added silicon material by feeding device, repeat step c, until reaching specified amount.
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| CN107128928B (en) * | 2017-05-25 | 2019-04-05 | 宁夏东梦能源股份有限公司 | Utilize the method for electron beam furnace purifying polycrystalline silicon |
| CN108101064B (en) * | 2017-12-23 | 2021-02-09 | 青岛蓝光晶科新材料有限公司 | Method for separating hard impurities in silicon by temperature gradient |
| CN112095019B (en) * | 2020-08-11 | 2021-07-30 | 大连理工大学 | Method for removing inclusions in high-temperature alloy through electron beam overheating dissolution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202267357U (en) * | 2011-08-03 | 2012-06-06 | 宁夏宁电光伏材料有限公司 | Water cooling device of graphite and coating substrate for electron beam melting |
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| JP2001294416A (en) * | 2000-04-07 | 2001-10-23 | Mitsubishi Materials Polycrystalline Silicon Corp | Device for producing polycrystalline silicon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202267357U (en) * | 2011-08-03 | 2012-06-06 | 宁夏宁电光伏材料有限公司 | Water cooling device of graphite and coating substrate for electron beam melting |
Non-Patent Citations (2)
| Title |
|---|
| 电子束熔炼多晶硅对杂质铝去除机制研究;姜大川 等;《材料工程》;20101231(第8期);第8-11页 * |
| 电子束熔炼提纯多晶硅中热量传输和能量利用的研究;温书涛;《中国硕士学位论文全文数据库 信息科技辑》;20130815(第08期);第I135-150页 * |
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