CN103741210B - A kind of electronic torch melting polysilicon deoxygenation and the method and apparatus of continuous casting - Google Patents
A kind of electronic torch melting polysilicon deoxygenation and the method and apparatus of continuous casting Download PDFInfo
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Abstract
The invention belongs to metallurgical smelting field, method and apparatus particularly to a kind of electronic torch melting polysilicon deoxygenation Yu continuous casting, the method, first by body of heater and electron gun evacuation, starts melting electron gun and polycrystalline silicon material is carried out electronic torch melting, and impurity oxygen is tentatively removed in melting；The further deoxygenation of liquid is kept under radiation electron gun effect, lead in ingot casting device finally by water-cooled transmission belt, it is oriented long brilliant casting ingot process, obtain polycrystalline silicon ingot casting, to all ingot casting devices, directional long crystal casting ingot process completes, this equipment includes electronic torch melting assembly and continuous casting assembly, the water-cooled transmission belt being provided with including melting kettle and this melting kettle side of water-cooled, ingot casting device is 36, it is fixedly installed on rotation platform, present invention firstly provides process and the purposes of electronic torch melting deoxygenation, achieve the effect of electron beam deoxygenation, in combination with continuous casting, reduce ingot casting and add the energy consumption needed for hot charge, substantially increase production efficiency.
Description
Technical field
The invention belongs to metallurgical smelting field, particularly to a kind of electronic torch melting polysilicon remove impurity and casting continuously
The method of ingot, additionally relates to its equipment.
Background technology
At present, China has become world energy sources production and consumption big country, but per capita energy's level of consumption is the lowest.
Along with the economic and development of society, China's energy demand is by sustainable growth, for current energy shortage
Situation, countries in the world are all carrying out deep thinking, and make great efforts to improve efficiency of energy utilization, promote renewable
The development and application of the energy, reduces the dependence to Imported oil, strengthens energy security.
The solar energy power generating development in recent years in one of the important development direction as regenerative resource is swift and violent,
Its proportion is increasing.According to " planning of regenerative resource Long-and Medium-term Development ", to the year two thousand twenty, China
Strive making solar electrical energy generation installed capacity reach 1.8GW(gigawatt), it is up to 600GW to the year two thousand fifty.
Expecting the year two thousand fifty, the electric power installation of China's regenerative resource will account for the 25% of whole nation electric power installation, Qi Zhongguang
Volt generator installation will account for 5%.Before anticipated the year two thousand thirty, the compound growth rate of China's solar energy installed capacity
Will be up to more than 25%.
The development of solar photovoltaic industry depends on the purification to polycrystalline silicon raw material.The purification work of polycrystalline silicon raw material
Skill currently mainly relies on following several technique: Siemens Method, silane thermal decomposition process, gas fluidized bed process and metallurgy method.
Metallurgy method prepares solar-grade polysilicon technology as development low cost, eco-friendly solar-grade polysilicon
The only way which must be passed of technology of preparing, has been achieved for tremendous development at present, and achieves industrialized production.Metallurgical
Method purifying polycrystalline silicon refers to use Physical Metallurgy means, in the case of silicon is not involved in chemical reaction, depends on
The method of the various impurity elements (phosphorus, boron and metal) in secondary removal silicon, it is not single preparation method, and
It is a kind of Integration Method, mainly utilizes saturated vapor pressure principle, segregation principle and oxidisability difference principle, respectively
Use different processes, remove the impurity element in silicon, thus it is pure to be met solar energy polycrystalline silicon
The silicon material that degree requires.
In metallurgy method technique, the phosphorus of silicon material, boron, metal impurities all can be gone by effective process means
Remove, reached comparatively ideal effect.But, in recent years, to polysilicon solar battery slice photoelectric conversion
The research of efficiency finds, the content of the oxygen element electricity conversion generation material impact to cell piece, one
As oxygen when being in interstitial site, the most do not show electroactive, but in casting polysilicon, oxygen concentration generally exist
3×1017～1.4 × 1018cm-3Between, the interstitial oxygen concentration of high concentration, during device fabrication subsequently, experiences
The heat treatment of various temperature, meeting segregation and precipitation in silicon crystal, form oxygen and close the defect such as alms giver, oxygen precipitation.
Meanwhile, under rapid owing to the solubility with temperature of oxygen reduces during silicon crystal material growth, cooling
Fall, oversaturated oxygen will form grown-in oxygen precipitates in casting polysilicon, it is also possible to is formed respectively with other impurity
Plant the complex of various kinds, such as N-O, C-O complex.These oxygen precipitations and complex thereof not only can reduce phosphorus
The effect of outer gettering, is even directly becoming the short-channel of battery.
These oxygen defects have the impact of favourable and unfavorable both sides to silicon materials and device, and it can be with colligator
Part technique forms intrinsic gettering, gettering metal impurity, it is also possible to pinning dislocation, improves the mechanical strength of silicon chip,
But other crystal defect can be induced again when oxygen precipitation excess, introduce substantial amounts of secondary defect, also can attract
The metallic elements such as ferrum, form ferrum oxygen precipitation complex, have the strongest few sub-compound ability, it is possible to significantly drop
The conversion efficiency of solar cell of low material.
In the techniques such as the directional solidification of metallurgy method, ingot casting, oxygen element in crucible or the oxygen being passed through in gas
Element inevitably enters in silicon material, is the main cause of oxygen impurities generation.In traditional test silicon
The common method of oxygen content is infrared spectrum, with infrared spectrum respectively to HIGH-PURITY SILICON material and batch mixing (after casting casting
Leftover pieces mix with high-purity material) detect, in two kinds of material, the content of oxygen is more or less the same, and this result also in smelting
The oxygen impurities introduced in gold method technique is not affected by paying attention to.
It practice, in silicon, oxygen element has two states: substitutes position, i.e. oxygen and instead of the position of silicon；Between
Gap position, i.e. oxygen is in the gap of silicon atom.Between in traditional test silicon, the infrared spectrum of oxygen content can only detect
The oxygen content of gap position, it is impossible to the oxygen levels in two kinds of silicon material of true reflection.Through the experiment test of applicant,
The oxygen substituting position can discharge electronics, similar to the effect that foreign matter of phosphor in silicon produces, it is possible to affect polycrystal silicon cell
Sheet electricity conversion.Applicant passes through ion microprobe repeated detection, in above two silicon material,
Oxygen element content differs greatly, and mainly substitutes the difference of the oxygen element content of position.Therefore, for ingot casting etc.
The impurity oxygen introduced in technique can not be ignored, it is necessary to seeks effective means and reduces the content of impurity oxygen in silicon.
But, in prior art, the best to the removal effect of oxygen element.For the minimizing technology of oxygen impurities,
Retrieve patent of invention CN200810070925 method reducing metal Oxygen in silicon, carbon content, this invention
Use in silicon liquid, be blown into oxygen, hydrogen and steam, make hydrogen and oxygen react generation local in silicon liquid
High temperature, makes the oxygen in silicon liquid, carbon remove with gas discharge, but the method needs in silicon molten
Being passed through oxygen and hydrogen under state, operation easier is big, and dangerous high, the removal effect of oxygen is the best.
Meanwhile, effectively in reduction polycrystalline silicon ingot casting raw material after oxygen content, can be obtained by directional long crystal technique
Obtaining polycrystalline silicon ingot casting, but casting ingot method before is all to directly heat ingot casting raw material, with duration, energy consumption is big,
Ingot casting list stove is carried out, it is impossible to realize continuous casting, needs extracting vacuum repeatedly, and energy consumption is the biggest.
Summary of the invention
In order to overcome above the deficiencies in the prior art, the present invention proposes a kind of electronic torch melting polysilicon deoxygenation
With the method for continuous casting, remove the impurity oxygen in polycrystalline silicon raw material by electronic torch melting, obtain high-purity low
The polysilicon liquid of oxygen, is guided directly into this polysilicon liquid continuous ingot-casting device and completes long brilliant casting ingot process,
Obtaining the polycrystalline silicon ingot casting of high-purity low-oxygen, the method effectively reduces the oxygen content in silicon material, improves battery
Conversion efficiency, decrease ingot casting raw material heating operation, this equipment install multiple ingot casting devices, can be real
Existing continuous casting effect, reduces the process time, reduces the total energy consumption in production process, cost-effective.
A kind of electronic torch melting polysilicon deoxygenation of the present invention and the method for continuous casting, first by body of heater
With electron gun evacuation, pre-thermionic electron guns；Then by feeding device in electron beam furnace melting kettle
Being continuously added to polycrystalline silicon material, start melting electron gun and polycrystalline silicon material is carried out electronic torch melting, melting is preliminary
Remove impurity oxygen；Polysilicon liquid after preliminary deoxygenation enters water-cooled transmission belt and in radiation with under electron gun effect
Keep the further deoxygenation of liquid, obtain the polysilicon liquid after deoxygenation；Finally the polysilicon liquid after deoxygenation is passed through
Flow-guiding mouth leads in ingot casting device, is oriented long brilliant casting ingot process, obtains polycrystalline silicon ingot casting, treat one
After platform ingot casting device directional long crystal casting ingot process completes, by rotate that rotation platform makes to be mounted thereon another
Individual ingot casting device is positioned at below flow-guiding mouth, proceeds directional long crystal casting ingot process, to all ingot casting devices
Directional long crystal casting ingot process completes.
Preferably follow the steps below:
(1) charging evacuation: put into charging by after polycrystalline silicon material cleaning, drying that granular size is 10-30mm
In device, bottom the silica crucible of ingot casting device, lay the polycrystalline silicon ingot casting bed material of 6N, and by body of heater and electricity
Sub-rifle evacuation, pre-thermionic electron guns 10-15min,；
(2) preliminary deoxygenation: be continuously added to step (1) in electron beam furnace melting kettle by feeding device
In polycrystalline silicon material, start melting electron gun, set the electron beam line of melting electron gun as
Impurity oxygen therein removed by 200-1200mA fusing melting polysilicon material；
(3) deoxygenation further: the polysilicon liquid after preliminary deoxygenation enters water-cooled transmission belt and at radiation electronics
Keep the further deoxygenation of liquid under rifle effect, obtain the polysilicon liquid after deoxygenation, set radiation during this and use
The electron beam line of electron gun is 200-800mA；
(4) polycrystalline silicon casting ingot process: add the 6N polycrystalline laid bottom the silica crucible of heat fusing ingot casting device
Silicon ingot casting bed material (mass fraction is 99.9999%), is led into the polysilicon liquid after deoxygenation by flow-guiding mouth
In the silica crucible of ingot casting device, the heater power controlling ingot casting device maintains polysilicon to be liquid, continuously
This polysilicon liquid is added in the silica crucible of ingot casting device, after reaching the 80%-85% of silica crucible volume,
Rotated by rotation platform and this ingot casting device be rotated away from and carried out directional long crystal casting ingot process, simultaneously another
Individual ingot casting device turns to below the flow-guiding mouth of water-cooled transmission belt；
(5) continuous casting: repeat the operation in step (2), (3) and (4), treat last
When polysilicon liquid after deoxygenation reaches the 80%-85% of its volume in ingot casting device silica crucible, stop electron beam
Melting, takes out polycrystalline silicon ingot casting after directional long crystal casting ingot process completes in all ingot casting devices, obtains electronics
The polycrystalline silicon ingot casting of bundle deoxygenation.
The vacuum of described body of heater is less than 5 × 10-2Pa, the vacuum of described electron gun is less than 5 × 10-3Pa。
Described polycrystalline silicon material purity is 99.996%-99.998%, and oxygen content is 4-20ppmw.
In described step (2), the smelting time of impurity oxygen therein removed by melting polysilicon material is 5-20min.
Electronic torch melting polysilicon deoxygenation of the present invention and the equipment of continuous casting, including body of heater, it is special
Levy and be: body of heater is provided with electronic torch melting assembly and continuous casting assembly, wherein:
Electronic torch melting assembly includes the melting kettle being installed on the water-cooled of body of heater internal upper part, on this melting kettle
Offering spill melting pond, this melting kettle side is provided with water-cooled transmission belt, and this water-cooled transmission belt side is with molten
Refining crucible side mouth is concordant, and opposite side is downward-sloping and is provided with flow-guiding mouth, solid on the body of heater of melting kettle top
Dingan County, equipped with melting electron gun, water-cooled transmission belt top body of heater is installed with radiation electron gun, position
Being provided with feeding device on the side furnace body wall of melting kettle, the discharging opening of this feeding device is positioned at melting earthenware
The top of crucible；
Continuous casting assembly includes the rotary shaft being installed on bottom of furnace body, and rotation platform is fixedly installed in rotary shaft
On, and rotate around rotation axis horizontal, on rotation platform, circle distribution formula is provided with ingot casting device, ingot casting
Device is positioned at below water-cooled transmission belt, and the vertical axis of the flow-guiding mouth position of water-cooled transmission belt is positioned at casting
Within the scope of the movement locus of ingot device.
Described water-cooled transmission belt is downward-sloping, and the angle of inclination between itself and horizontal plane is 5 °～15 °, water-cooled
Transmission belt monomer molding or with melting kettle global formation.
Ingot casting device is 3-6 platform, is fixedly installed on rotation platform.
Ingot casting device includes the magnetism servo-electric motor water-cooling being fixedly installed on rotation platform, and this magnetism servo-electric motor water-cooling is provided with quartz
Crucible, silica crucible outer wall is provided with heater and insulation sleeve from inside to outside.
In the present invention, propose process and the purposes of electronic torch melting deoxygenation first, utilize electron beam
Melting high temperature evaporation goes deimpurity characteristic, is melted in melting kettle by melting electron gun and at the beginning of melting
Step deoxygenation, the highest under the effect of radiation electron gun on the large surface area in water-cooled transmission belt
Effect deoxygenation, and maintain liquid to enter in ingot casting device, the liquid high purity polycrystalline silicon of hypoxia is provided for casting ingot process
Raw material, arranges multiple ingot casting device in the equipment of proposition, after an ingot casting device completes casting ingot process, and rotation
Turn next ingot casting device receive hypoxia polysilicon liquid and carry out directional long crystal casting ingot process, it is achieved that cast continuously
The effect of ingot, present invention achieves the effect of electron beam deoxygenation, in combination with continuous casting, decreases electronics
After bundle melting, solidification and ingot casting add the time of hot charge, reduce ingot casting and add the energy consumption needed for hot charge, significantly
Improve production efficiency.
It is an advantage of the current invention that:
(1) propose process and the purposes of electron beam deoxygenation, solve what impurity oxygen in polysilicon was removed
A difficult problem, oxygen content can be reduced to 0.0571ppmw, meets solaode to polycrystalline silicon ingot casting oxygen content
Requirement.
(2) removed further by radiating electron bundle when achieving the preliminary deoxygenation of melting and the flowing of polysilicon liquid
Oxygen, shortens the deoxygenation time more than 20%.
(3) electronic torch melting deoxygenation technology couples with serialization ingot casting technology, it is achieved continuous prodution, can carry
High efficiency more than 50%, energy efficient more than 25%.
Accompanying drawing explanation
Fig. 1 is the structural representation of the present invention；
In figure: 1, body of heater 2, melting kettle 3, melting electron gun 4, radiation electron gun 5,
Feeding device 6, silica crucible 7, magnetism servo-electric motor water-cooling 8, heater 9, insulation sleeve 10,
Rotation platform 11, rotary shaft 12, water-cooled transmission belt 13, flow-guiding mouth
Detailed description of the invention
Describe the present invention in detail below in conjunction with specific embodiments and the drawings, but the invention is not limited in concrete reality
Execute example.
Embodiment 1:
As it is shown in figure 1, electronic torch melting polysilicon deoxygenation and the equipment of continuous casting, including body of heater, body of heater 1
In be provided with electronic torch melting assembly and continuous casting assembly, wherein:
Electronic torch melting assembly includes the melting kettle 2 being installed on the water-cooled of body of heater internal upper part, on this melting kettle
Offering spill melting pond (not pointing out in accompanying drawing), this melting kettle side is provided with water-cooled transmission belt 12, this water
Cold transmission belt side is concordant with melting kettle side mouth, and opposite side is downward-sloping and is provided with flow-guiding mouth 13, water
Baltimore groove is had, for guiding the polysilicon liquid of preliminary for melting deoxygenation to the side of ingot casting device in cold transmission belt
To flowing, and enter in ingot casting device by the flow-guiding mouth in water-cooled transmission belt, on the body of heater of melting kettle top
Being installed with melting electron gun 3, this used in electron gun is tentatively removed in melting oxygen content more much higher crystal silicon material
Impurity oxygen therein, water-cooled transmission belt top body of heater is installed with radiation electron gun 4, is positioned at melting earthenware
Being provided with feeding device 5 on the side furnace body wall of crucible, the discharging opening of this feeding device is positioned at the upper of melting kettle
Side.
Melting electron gun goes the removal of impurity for melting polysilicon material, and after a period of time, silicon liquid stream enters water-cooled and passes
The Baltimore groove of defeated band, this Baltimore groove surface area is relatively big, silicon liquid tile its upper after beneficially rapid impurity removal, water-cooled
Transmission belt monomer molding, melting kettle and water-cooled transmission belt are made up of copper product, are wherein passed through recirculated cooling water,
To avoid fusing and to damage, water-cooled transmission belt is downward-sloping, and the angle of inclination between itself and horizontal plane is 5 °,
So that silicon liquid flows downward smoothly along Baltimore groove in water-cooled transmission belt, and enters ingot casting device by flow-guiding mouth
In silica crucible in.
Continuous casting assembly includes the rotary shaft 11 being installed on bottom of furnace body, logical between rotary shaft and bottom of furnace body
Cross movable sealing to connect, to ensure the sealing of body of heater, it is possible to realize the rotation of horizontal steady circular, circumference
Movement rate controls at 10mm/s-50mm/s, and rotation platform 10 is fixedly installed in rotary shaft, can be around
Rotation axis horizontal rotates, and on rotation platform, circle distribution formula is provided with ingot casting device, each two ingot casting device
Between angle equal, ingot casting device is positioned at below water-cooled transmission belt, and the flow-guiding mouth place of water-cooled transmission belt
Within the scope of the vertical axis of position is positioned at the movement locus of ingot casting device, to ensure the silicon flowed out from flow-guiding mouth
Liquid adds in the silica crucible of ingot casting device smoothly.
Ingot casting device is 6, and circle distribution formula is fixedly installed on rotation platform, every two ingot casting devices it
Between angle be 60 °, ingot casting device includes the magnetism servo-electric motor water-cooling being fixedly installed on rotation platform, this water cooling unit
Structure is provided with silica crucible, and silica crucible outer wall is provided with heater and insulation sleeve, water cooling unit from inside to outside
Structure can use water-cooled ingot pulling mechanism, the graphite heater that the heater now used is integrated, by heating
Keep liquid and draw ingot to realize directional long crystal technique；Fixing magnetism servo-electric motor water-cooling can also be used, now use
The graphite heater that heater is split, this graphite heater is divided into three, upper, middle and lower graphite heating sheet,
Being oriented crystal growing technology by the heating power of the graphite heating sheet of regulation upper, middle and lower, this ingot casting fills
Put all processes that can realize directional long crystal casting ingot process.
Embodiment 2:
Use the device described in embodiment 1, carry out electronic torch melting polysilicon deoxygenation and continuous casting technique,
Specifically comprise the following steps that
(1) charging evacuation: by granular size be 10-12mm, purity be 99.996%, oxygen content be
Put in feeding device after the polycrystalline silicon material cleaning, drying of 20ppmw, spread bottom the silica crucible of ingot casting device
If the polycrystalline silicon ingot casting bed material of 6N, and the vacuum of body of heater is evacuated to 3 × 10-2Pa, the vacuum of electron gun
It is evacuated to 4 × 10-3Pa, pre-thermionic electron guns 15min；
(2) preliminary deoxygenation: be continuously added to step (1) in electron beam furnace melting kettle by feeding device
In polycrystalline silicon material, start melting electron gun, set the electron beam line of melting electron gun as 1200mA
Fusing melting 15min polycrystalline silicon material tentatively remove impurity oxygen therein；
(3) deoxygenation further: the polysilicon liquid after preliminary deoxygenation enters water-cooled transmission belt and at radiation electronics
Keep the further deoxygenation of liquid under rifle effect, obtain the polysilicon liquid after deoxygenation, set radiation during this and use
The electron beam line of electron gun is 800mA；
(4) polycrystalline silicon casting ingot process: add the 6N(matter laid bottom the silica crucible of heat fusing ingot casting device
Amount mark is 99.9999%) polycrystalline silicon ingot casting bed material becomes liquid, the polysilicon liquid after deoxygenation passed through
Flow-guiding mouth leads in the silica crucible of ingot casting device, and the heater power controlling ingot casting device maintains these many
Crystal silicon liquid is liquid, adds this polysilicon liquid continuously in the silica crucible of ingot casting device, to reaching quartz earthenware
After the 80% of crucible volume, rotated by rotation platform and this ingot casting device is rotated away from and carries out directional long crystal casting
Ingot technique, controlling directional long crystal speed during this is 1.2cm-1.3cm/h (centimetre per hour), simultaneously another
Individual ingot casting device turns to below water-cooled transmission belt flow-guiding mouth；
(5) continuous casting: repeat the operation in step (2), (3) and (4), treat last
When polysilicon liquid after deoxygenation reaches the 80% of its volume in ingot casting device silica crucible, stop electronic torch melting,
After directional long crystal casting ingot process completes in all ingot casting devices, take out polycrystalline silicon ingot casting, obtain electron beam deoxygenation
Polycrystalline silicon ingot casting, this polycrystalline silicon ingot casting through secondary ion mass spectrum (SIMS) detect, its oxygen content be less than two
The secondary ion Mass Spectrometer Method limit, i.e. less than 0.0571ppmw.
Embodiment 3:
Use the device described in embodiment 1, carry out electronic torch melting polysilicon deoxygenation and continuous casting technique,
Specifically comprise the following steps that
(1) charging evacuation: by granular size be 24-30mm, purity be 99.997%, oxygen content be
Put in feeding device after the polycrystalline silicon material cleaning, drying of 11ppmw, spread bottom the silica crucible of ingot casting device
If the polycrystalline silicon ingot casting bed material of 6N, and the vacuum of body of heater is evacuated to 4 × 10-2Pa, the vacuum of electron gun
It is evacuated to 4.5 × 10-3Pa, pre-thermionic electron guns 13min；
(2) preliminary deoxygenation: be continuously added to step (1) in electron beam furnace melting kettle by feeding device
In polycrystalline silicon material, start melting electron gun, set the electron beam line of melting electron gun as 800mA
Fusing melting 5min polycrystalline silicon material tentatively remove impurity oxygen therein；
(3) deoxygenation further: the polysilicon liquid after preliminary deoxygenation enters water-cooled transmission belt and at radiation electronics
Keep the further deoxygenation of liquid under rifle effect, obtain the polysilicon liquid after deoxygenation, set radiation during this and use
The electron beam line of electron gun is 500mA；
(4) polycrystalline silicon casting ingot process: add the 6N polycrystalline laid bottom the silica crucible of heat fusing ingot casting device
Silicon ingot casting bed material is liquid, and the polysilicon liquid after deoxygenation leads into the stone of ingot casting device by flow-guiding mouth
In English crucible, the heater power controlling ingot casting device maintains this polysilicon liquid to be liquid, fills to ingot casting continuously
The silica crucible put adds this polysilicon liquid, to reach silica crucible volume 82% after, pass through rotary flat
Platform rotates and is rotated away from by this ingot casting device and carries out directional long crystal casting ingot process, controls orientation long during this
Brilliant speed is 1.2cm-1.3cm/h (centimetre per hour), and another ingot casting device turns to water-cooled transmission belt simultaneously
Below flow-guiding mouth；
(5) continuous casting: repeat the operation in step (2), (3) and (4), treat last
When polysilicon liquid after deoxygenation reaches the 82% of its volume in ingot casting device silica crucible, stop electronic torch melting,
After directional long crystal casting ingot process completes in all ingot casting devices, take out polycrystalline silicon ingot casting, obtain electron beam deoxygenation
Polycrystalline silicon ingot casting, this polycrystalline silicon ingot casting through secondary ion mass spectrum (SIMS) detect, its oxygen content be less than two
The secondary ion Mass Spectrometer Method limit, i.e. less than 0.0571ppmw.
Embodiment 4
Use the device described in embodiment 1, carry out electronic torch melting polysilicon deoxygenation and continuous casting technique,
Specifically comprise the following steps that
(1) charging evacuation: by granular size be 15-20mm, purity be 99.998%, oxygen content be 4ppmw
Polycrystalline silicon material cleaning, drying after put in feeding device, bottom the silica crucible of ingot casting device lay 6N
Polycrystalline silicon ingot casting bed material, and the vacuum of body of heater is evacuated to 4.5 × 10-2Pa, the vacuum of electron gun is evacuated to
4.7×10-3Pa, pre-thermionic electron guns 10min；
(2) preliminary deoxygenation: be continuously added to step (1) in electron beam furnace melting kettle by feeding device
In polycrystalline silicon material, start melting electron gun, set the electron beam line of melting electron gun as 200mA
Fusing melting 20min polycrystalline silicon material tentatively remove impurity oxygen therein；
(3) deoxygenation further: the polysilicon liquid after preliminary deoxygenation enters water-cooled transmission belt and at radiation electronics
Keep the further deoxygenation of liquid under rifle effect, obtain the polysilicon liquid after deoxygenation, set radiation during this and use
The electron beam line of electron gun is 200mA；
(4) polycrystalline silicon casting ingot process: add the 6N polycrystalline laid bottom the silica crucible of heat fusing ingot casting device
Silicon ingot casting bed material, the polysilicon liquid after deoxygenation leads in the silica crucible of ingot casting device by flow-guiding mouth,
The heater power controlling ingot casting device maintains this polysilicon liquid to be liquid, continuously to the quartzy earthenware of ingot casting device
Crucible adds this polysilicon liquid, to reach silica crucible volume 85% after, by rotation platform rotate should
Ingot casting device is rotated away from and carries out directional solidification casting ingot process, controls directional long crystal speed and be during this
1.2cm-1.3cm/h (centimetre per hour), under another ingot casting device turns to water-cooled transmission belt flow-guiding mouth simultaneously
Side；
(5) continuous casting: repeat the operation in step (2), (3) and (4), treat last
When polysilicon liquid after deoxygenation reaches the 85% of its volume in ingot casting device silica crucible, stop electronic torch melting,
After directional solidification casting ingot process completes in all ingot casting devices, take out polycrystalline silicon ingot casting, obtain electron beam deoxygenation
Polycrystalline silicon ingot casting, this polycrystalline silicon ingot casting through secondary ion mass spectrum (SIMS) detect, its oxygen content be less than two
The secondary ion Mass Spectrometer Method limit, i.e. less than 0.0571ppmw.
Claims (9)
1. an electronic torch melting polysilicon deoxygenation and the method for continuous casting, it is characterised in that: first will
Body of heater and electron gun evacuation, pre-thermionic electron guns；Then by feeding device to electron beam furnace melting
Crucible is continuously added to polycrystalline silicon material, starts melting electron gun and polycrystalline silicon material is carried out electronic torch melting,
Impurity oxygen is tentatively removed in melting；Polysilicon liquid after preliminary deoxygenation enters water-cooled transmission belt and in radiation electricity consumption
Keep the further deoxygenation of liquid under sub-rifle effect, obtain the polysilicon liquid after deoxygenation；Finally by after deoxygenation
Polysilicon liquid leads in ingot casting device by flow-guiding mouth, is oriented long brilliant casting ingot process, obtains many
Crystal silicon ingot casting, after an ingot casting device directional long crystal casting ingot process completes, makes by rotating rotation platform
Another ingot casting device being mounted thereon is positioned at below flow-guiding mouth, proceeds directional long crystal casting ingot process,
To all ingot casting devices, directional long crystal casting ingot process completes.
A kind of electronic torch melting polysilicon deoxygenation the most according to claim 1 and the side of continuous casting
Method, it is characterised in that specifically comprise the following steps that
(1) charging evacuation: add putting into after polycrystalline silicon material cleaning, drying that granular size is 10-30mm
In material device, bottom the silica crucible of ingot casting device, lay the polycrystalline silicon ingot casting bed material of 6N, and by body of heater
With electron gun evacuation, pre-thermionic electron guns 10-15min；
(2) preliminary deoxygenation: be continuously added to step in electron beam furnace melting kettle by feeding device
(1) polycrystalline silicon material in, starts melting electron gun, set the electron beam line of melting electron gun as
Impurity oxygen therein tentatively removed by 200-1200mA fusing melting polysilicon material；
(3) deoxygenation further: the polysilicon liquid after preliminary deoxygenation enters water-cooled transmission belt and in radiation electricity consumption
Keep the further deoxygenation of liquid under sub-rifle effect, obtain the polysilicon liquid after deoxygenation, during this, set spoke
Penetrating with the electron beam line of electron gun is 200-800mA；
(4) polycrystalline silicon casting ingot process: add the 6N laid bottom the silica crucible of heat fusing ingot casting device many
Crystal silicon ingot casting bed material, leads into the quartzy earthenware of ingot casting device by the polysilicon liquid after deoxygenation by flow-guiding mouth
In crucible, the heater power controlling ingot casting device maintains polysilicon to be liquid, continuously to the stone of ingot casting device
English crucible adds this polysilicon liquid, after reaching the 80%-85% of silica crucible volume, passes through rotary flat
Platform rotates and this ingot casting device is rotated away from and is carried out directional long crystal casting ingot process, another ingot casting dress simultaneously
Put and turn to below the flow-guiding mouth of water-cooled transmission belt；
(5) continuous casting: repeat the operation in step (2), (3) and (4), treat last
When polysilicon liquid after deoxygenation reaches the 80%-85% of its volume in individual ingot casting device silica crucible, stop electricity
Son bundle melting, takes out polycrystalline silicon ingot casting after directional long crystal casting ingot process completes in all ingot casting devices,
Polycrystalline silicon ingot casting to electron beam deoxygenation.
3. according to the arbitrary described a kind of electronic torch melting polysilicon deoxygenation of claim 1 or 2 and casting continuously
The method of ingot, it is characterised in that: the vacuum of described body of heater is less than 5 × 10-2Pa, described electron gun true
Reciprocal of duty cycle is less than 5 × 10-3Pa。
4. according to the arbitrary described a kind of electronic torch melting polysilicon deoxygenation of claim 1 or 2 and casting continuously
The method of ingot, it is characterised in that: described polycrystalline silicon material purity is 99.996%-99.998%, and oxygen content is
4-20ppmw。
A kind of electronic torch melting polysilicon deoxygenation the most according to claim 2 and the method for continuous casting,
It is characterized in that: in described step (2), the smelting time of melting polysilicon material removal impurity oxygen therein is
5-20min。
6. the deoxygenation of electronic torch melting polysilicon and an equipment for continuous casting, including body of heater, its feature exists
In: body of heater is provided with electronic torch melting assembly and continuous casting assembly, wherein:
Electronic torch melting assembly includes the melting kettle being installed on the water-cooled of body of heater internal upper part, this melting kettle
On offer spill melting pond, this melting kettle side is provided with water-cooled transmission belt, this water-cooled transmission belt side
Concordant with melting kettle side mouth, opposite side is downward-sloping and is provided with flow-guiding mouth, melting kettle top stove
It is installed with melting electron gun on body, water-cooled transmission belt top body of heater is installed with radiation electricity consumption
Sub-rifle, is positioned on the side furnace body wall of melting kettle and is provided with feeding device, the discharging opening of this feeding device
It is positioned at the top of melting kettle；
Continuous casting assembly includes the rotary shaft being installed on bottom of furnace body, and rotation platform is fixedly installed in rotation
On axle, and around rotation axis horizontal rotate, on rotation platform circle distribution formula ingot casting device is installed,
Ingot casting device is positioned at below water-cooled transmission belt, and the vertical axis of the flow-guiding mouth position of water-cooled transmission belt
Within the scope of being positioned at the movement locus of ingot casting device；Ingot casting device includes being fixedly installed on rotation platform
Magnetism servo-electric motor water-cooling, magnetism servo-electric motor water-cooling is provided with silica crucible, and silica crucible outer wall is provided with heater from inside to outside
With insulation sleeve.
A kind of electronic torch melting polysilicon deoxygenation the most according to claim 6 and the equipment of continuous casting,
It is characterized in that: described water-cooled transmission belt is downward-sloping, the angle of inclination between itself and horizontal plane be 5 °～
15°。
8. according to the arbitrary described a kind of electronic torch melting polysilicon deoxygenation of claim 6 or 7 and casting continuously
The equipment of ingot, it is characterised in that: described water-cooled transmission belt monomer molding or with melting kettle global formation.
A kind of electronic torch melting polysilicon deoxygenation the most according to claim 6 and the equipment of continuous casting,
It is characterized in that: described ingot casting device is 3-6 platform, is fixedly installed on rotation platform.
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| CN104532340A (en) * | 2014-12-24 | 2015-04-22 | 大连理工大学 | Device and method for electron beam melting and single-crystal lifting coupling |
| CN105951180B (en) * | 2016-06-01 | 2019-03-15 | 江苏协鑫硅材料科技发展有限公司 | Polycrystalline silicon ingot or purifying furnace secondary charging device and polycrystalline cast ingot system |
| CN106894084A (en) * | 2017-01-16 | 2017-06-27 | 大工（青岛）新能源材料技术研究院有限公司 | A kind of method for changing electron beam purifying polycrystalline silicon solidification crucible shop fixtures mode |
| CN109023521A (en) * | 2018-08-29 | 2018-12-18 | 孟静 | The preparation method of solar cell module polysilicon chip |
| CN112111658B (en) * | 2020-08-27 | 2022-07-05 | 宁波创润新材料有限公司 | Smelting method of granular material |
| CN114086240A (en) * | 2021-11-09 | 2022-02-25 | 北京华卓精科科技股份有限公司 | Annular crucible, and crystal transverse directional growth device and method |
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