CN103741210A - Method and device for electron beam melting to remove oxygen from polysilicon and continuous ingot casting - Google Patents
Method and device for electron beam melting to remove oxygen from polysilicon and continuous ingot casting Download PDFInfo
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Abstract
Belonging to the field of metallurgical melting, the invention in particular relates to a method and a device for electron beam melting to remove oxygen from polysilicon and continuous ingot casting. The method includes: subjecting a furnace body and an electron gun to vacuum pumping, starting a electron gun for melting to conduct electron beam melting on a polysilicon material, and preliminarily removing impurity oxygen; under the action of an electron gun for radiation, keeping a liquid state and further conducting oxygen removal, and finally leading the polysilicon liquid into ingot casting equipment through a water-cooled transmission belt to carry out a directional crystal growth ingot casting process so as to obtain a polysilicon cast ingot till the end of directional crystal growth ingot casting processes in all ingot casting equipment. The device includes an electron beam melting assembly and a continuous ingot casting assembly. The electron beam melting assembly comprises a water-cooled melting crucible and the water-cooled transmission belt disposed on one side of the melting crucible. 3-6 ingot casting equipment is fixedly mounted on a rotating platform. The invention puts forward the technological method and application of electron beam melting for oxygen removal, realizes the effects of oxygen removal by electron beams. At the same time, by combining continuous ingot casting, the energy consumption needed by heating the raw materials of ingot casting is reduced, and the production efficiency is greatly improved.
Description
Technical field
The invention belongs to metallurgical smelting field, particularly the method for the removal of impurities of a kind of electron beam melting polysilicon and continuous casting, also relates to its equipment in addition.
Background technology
At present, China has become world energy sources production and consumption big country, but energy expenditure level is also very low per capita.Along with economical and social development, China's energy demand is by sustainable growth, for current energy shortage situation, deep thinking is all being carried out in countries in the world, and effort improves efficiency of energy utilization, promote the development and application of renewable energy source, reduce the dependence to Imported oil, strengthen energy security.
Solar energy power generating development in recent years as one of important development direction of renewable energy source is swift and violent, and its proportion is increasing.According to < < renewable energy source Long-and Medium-term Development planning > >, to the year two thousand twenty, China strives making solar electrical energy generation installed capacity to reach 1.8GW(gigawatt), will reach 600GW to the year two thousand fifty.Expect the year two thousand fifty, the electric power installation of Chinese renewable energy source will account for 25% of national electric power installation, and wherein photovoltaic generation installation will account for 5%.Before estimating the year two thousand thirty, the compound growth rate of Chinese sun power installed capacity will be up to more than 25%.
The development of photovoltaic industry depends on the purification to polycrystalline silicon raw material.The purifying technique of polycrystalline silicon raw material is several technique below main dependence at present: Siemens Method, silane thermal decomposition process, gas fluidized bed method and metallurgy method.Metallurgy method is prepared solar-grade polysilicon technology as the only way which must be passed of development low cost, eco-friendly solar-grade polysilicon technology of preparing, has obtained at present tremendous development, and has realized suitability for industrialized production.Metallurgy method purifying polycrystalline silicon refers to the physical metallurgy means that adopt, in the situation that silicon does not participate in chemical reaction occurs, remove successively the method for the various impurity elements (phosphorus, boron and metal) in silicon, it is not single preparation method, but a kind of Integration Method mainly utilizes saturated vapor pressure principle, segregation principle and oxidisability difference principle, adopts respectively different processing methodes, the impurity element of making a return journey in silica removal, thus be met the silicon material of solar energy polycrystalline silicon purity requirement.
In metallurgy method technique, the phosphorus of silicon material, boron, metal impurities all can be removed by effective process means, have reached comparatively ideal effect.But, in recent years, in to the research of polysilicon solar battery slice electricity conversion, find, the content of oxygen element produces material impact to the electricity conversion of cell piece, general oxygen is when interstitial site, conventionally aobvious electroactive, however in casting polycrystalline silicon oxygen concn conventionally 3 * 10
17～1.4 * 10
18cm
-3between, the interstitial oxygen concentration of high density, in device fabrication process subsequently, experiences the thermal treatment of all temps, and meeting segregation and precipitation in silicon crystal form oxygen and close the defects such as alms giver, oxygen precipitation.Simultaneously, solubility with temperature due to oxygen in silicon crystal material growth, cooling process reduces and declines rapidly, oversaturated oxygen will form primary oxygen precipitation in casting polycrystalline silicon, also may form various complex bodys with other impurity, as N-O, C-O complex body.These oxygen precipitations and complex body thereof not only can reduce the effect of the outer gettering of phosphorus, even directly become the short-channel of battery.
These oxygen defects have the impact of favourable and unfavorable two aspects on silicon materials and device, it can form intrinsic gettering in conjunction with device technology, absorb metallic impurity, all right pinning dislocation, the physical strength of raising silicon chip, but can induce other lattice defect again when oxygen precipitation is excessive, introduce a large amount of secondary defects, also can attract the metallic elements such as iron, form iron oxygen precipitation complex body, there is very strong few sub-compound ability, can significantly reduce the conversion efficiency of solar cell of material.
In the techniques such as the directional freeze of metallurgy method, ingot casting, the oxygen element in crucible or the oxygen element passing in gas inevitably can enter into silicon material, are the major causes that oxygen impurities produces.In traditional test silicon, the common method of oxygen level is infrared spectra, with infrared spectra, respectively HIGH-PURITY SILICON material is detected with batch mixing (scrap stock after casting casting mix with high-purity material), in two kinds of material, the content of oxygen is more or less the same, and this has also caused the oxygen impurities of introducing in metallurgy method technique not come into one's own.
In fact, in silicon, oxygen element has two states: substitute position, oxo has been replaced the position of silicon; Gap digit, oxygen is in the gap of Siliciumatom.The oxygen level that in traditional test silicon, the infrared spectra of oxygen level can only detector gap position, can not truly reflect two kinds of oxygen levels in silicon material.Through applicant's experiment test, the oxygen that substitutes position can discharge electronics, similar to the effect that foreign matter of phosphor in silicon produces, and can affect polycrystalline silicon battery plate electricity conversion.Applicant is by sims repeated detection, and in above-mentioned two kinds of silicon material, oxygen element content differs greatly, and is mainly the difference that substitutes the oxygen element content of position.Therefore, for the impurity oxygen of introducing in the techniques such as ingot casting, can not ignore, must seek the content that effective means reduce impurity oxygen in silicon.
But, in prior art, not good to the removal effect of oxygen element.Removal method for oxygen impurities, retrieve patent of invention CN200810070925 method that reduces oxygen in Pure Silicon Metal, carbon content, this invention adopts and in silicon liquid, is blown into oxygen, hydrogen and water vapour, hydrogen and oxygen are reacted in silicon liquid and produce localized hyperthermia, oxygen, carbon in silicon liquid are removed with gaseous emission, but the method need to pass into oxygen and hydrogen under silicon molten state, operation easier is large, dangerous high, the removal effect of oxygen is not good.
Simultaneously, effectively reduce in polycrystalline silicon ingot casting raw material after oxygen level, can obtain polycrystalline silicon ingot casting by directional long crystal technique, but casting ingot method is before all direct heating ingot casting raw material, with duration, energy consumption is large, ingot casting list stove carries out, can not realize continuous casting, need extracting vacuum repeatedly, energy consumption is also larger.
Summary of the invention
In order to overcome above the deficiencies in the prior art, the present invention proposes the method for the deoxygenation of a kind of electron beam melting polysilicon and continuous casting, by electron beam melting, remove the impurity oxygen in polycrystalline silicon raw material, obtain the polysilicon liquid of high-purity low-oxygen, the direct guiding of this polysilicon liquid is entered to continuous ingot-casting device and complete long brilliant casting ingot process, obtain the polycrystalline silicon ingot casting of high-purity low-oxygen, the method effectively reduces the oxygen level in silicon material, improved the efficiency of conversion of battery, reduced the operation of ingot casting heating raw materials, a plurality of ingot casting devices that this equipment is installed, can realize continuous casting effect, reduce the process time, reduce the total energy consumption in production process, save cost.
The method of a kind of electron beam melting polysilicon of the present invention deoxygenation and continuous casting, first vacuumizes body of heater and electron beam gun, pre-thermionic electron guns; Then by feeding device, in electron beam melting furnace smelting pot, add continuously polycrystalline silicon material, start melting, with electron beam gun, polycrystalline silicon material is carried out to electron beam melting, impurity oxygen is tentatively removed in melting; Polysilicon liquid after preliminary deoxygenation enters water-cooled transport tape and in the liquid further deoxygenation of maintenance under electron beam gun effect for radiation, obtains the polysilicon liquid after deoxygenation; Finally the polysilicon liquid after deoxygenation is guided and entered in ingot casting device by flow-guiding mouth, carry out directional long crystal casting ingot process, obtain polycrystalline silicon ingot casting, after an ingot casting device directional long crystal casting ingot process completes, by rotating rotation platform, make another ingot casting device being mounted thereon be positioned at flow-guiding mouth below, proceed directional long crystal casting ingot process, extremely in all ingot casting devices, directional long crystal casting ingot process completes.
Preferably according to following steps, carry out:
(1) charging vacuumizes: after the polycrystalline silicon material cleaning, drying that is 10-30mm by granular size, put into feeding device, in the quartz crucible bottom of ingot casting device, lay the polycrystalline silicon ingot casting bed material of 6N, and body of heater and electron beam gun are vacuumized, pre-thermionic electron guns 10-15min;
(2) preliminary deoxygenation: add continuously the polycrystalline silicon material in step (1) by feeding device in electron beam melting furnace smelting pot, start melting electron beam gun, setting melting is that 200-1200mA fusing melting polysilicon material are removed impurity oxygen wherein with the electron beam line of electron beam gun;
(3) further deoxygenation: the polysilicon liquid after preliminary deoxygenation enters water-cooled transport tape and the liquid further deoxygenation of maintenance under electron beam gun effect for radiation, obtain the polysilicon liquid after deoxygenation, in this process, setting radiation is 200-800mA with the electron beam line of electron beam gun;
(4) polycrystalline silicon casting ingot process: the 6N polycrystalline silicon ingot casting bed material (massfraction is 99.9999%) that lay the quartz crucible bottom of heat fused ingot casting device, polysilicon liquid after deoxygenation is guided in the quartz crucible that enters ingot casting device by flow-guiding mouth, the heater power of controlling ingot casting device maintains polysilicon for liquid, in the quartz crucible of ingot casting device, add this polysilicon liquid continuously, to reaching after the 80%-85% of quartz crucible volume, by rotation platform, rotate and the rotation of this ingot casting device is left and carried out directional long crystal casting ingot process, another ingot casting device turns to the flow-guiding mouth below of water-cooled transport tape simultaneously,
(5) continuous casting: repeat the operation in step (2), (3) and (4), when the polysilicon liquid after deoxygenation in last ingot casting device quartz crucible reaches the 80%-85% of its volume, stop electron beam melting, until directional long crystal casting ingot process in all ingot casting devices, after completing, take out polycrystalline silicon ingot casting, obtain the polycrystalline silicon ingot casting of electron beam deoxygenation.
The low vacuum of described body of heater is in 5 * 10
-2pa, the low vacuum of described electron beam gun is in 5 * 10
-3pa.
Described polycrystalline silicon material purity is 99.996%-99.998%, and oxygen level is 4-20ppmw.
In described step (2), the smelting time of melting polysilicon material removal impurity oxygen is wherein 5-20min.
The equipment of electron beam melting polysilicon of the present invention deoxygenation and continuous casting, comprises body of heater, it is characterized in that: in body of heater, be provided with electron beam melting assembly and continuous casting assembly, wherein:
Electron beam melting assembly comprises the smelting pot of the water-cooled that is installed on body of heater internal upper part, on this smelting pot, offer spill melting pond, this smelting pot one side is provided with water-cooled transport tape, this water-cooled transport tape one side is concordant with smelting pot side mouth, opposite side is downward-sloping and be provided with flow-guiding mouth, on the body of heater of smelting pot top, be installed with melting electron beam gun, on the body of heater of water-cooled transport tape top, be installed with radiation electron beam gun, be positioned on a wing furnace body wall of smelting pot and be provided with feeding device, the discharge port of this feeding device is positioned at the top of smelting pot;
Continuous casting assembly comprises the turning axle that is installed on bottom of furnace body, rotation platform is fixedly installed on turning axle, and horizontally rotate around turning axle, on rotation platform, circle distribution formula is provided with ingot casting device, ingot casting device is positioned at water-cooled transport tape below, and within the vertical axis of the flow-guiding mouth position of water-cooled transport tape is positioned at the movement locus scope of ingot casting device.
Described water-cooled transport tape is downward-sloping, and the angle of inclination between itself and horizontal plane is 5 °～15 °, the monomer moulding of water-cooled transport tape or with smelting pot global formation.
Ingot casting device is 3-6 platform, is fixedly installed on rotation platform.
Ingot casting device comprises 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, is provided with from inside to outside well heater and insulation sleeve on quartz crucible outer wall.
In the present invention, processing method and the purposes of electron beam melting deoxygenation have been proposed first, utilize electron beam melting high temperature evaporation to go deimpurity characteristic, by melting, use electron beam gun to melt in smelting pot and the preliminary deoxygenation of melting, further efficient deoxygenation under the effect of electron beam gun of radiation use on large surface area on water-cooled transport tape, and maintain liquid state and enter in ingot casting device, for casting ingot process provides the liquid high-purity polycrystalline silicon raw material of hypoxemia, in the equipment proposing, a plurality of ingot casting devices are set, at an ingot casting device, complete after casting ingot process, rotating next ingot casting device receives hypoxemia polysilicon liquid and carries out directional long crystal casting ingot process, realized the effect of continuous casting, the present invention has realized the effect of electron beam deoxygenation, simultaneously in conjunction with continuous casting, reduced the time of electron beam melting after coagulation and ingot casting heating raw, reduced the required energy consumption of ingot casting heating raw, greatly improved production efficiency.
The invention has the advantages that:
(1) proposed processing method and the purposes of electron beam deoxygenation, solved the difficult problem that in polysilicon, impurity oxygen is removed, oxygen level can be reduced to 0.0571ppmw, meets the requirement of solar cell to polycrystalline silicon ingot casting oxygen level.
(2) realized when the preliminary deoxygenation of melting and polysilicon are liquid to flow by the further deoxygenation of radiating electron bundle, shortened the deoxygenation time more than 20%.
(3) electron beam melting deoxygenation technology and the coupling of serialization ingot casting technology, realize serialization and produce, and can enhance productivity more than 50%, and energy efficient is more than 25%.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention;
In figure: 1, body of heater 2, smelting pot 3, electron beam gun 4 for melting, electron beam gun 5, feeding device 6, quartz crucible 7, magnetism servo-electric motor water-cooling 8, well heater 9, insulation sleeve 10, rotation platform 11, turning axle 12, water-cooled transport tape 13, flow-guiding mouth for radiation
Embodiment
Below in conjunction with specific embodiments and the drawings, describe the present invention in detail, but the present invention is not limited to specific embodiment.
Embodiment 1:
As shown in Figure 1, the equipment of the deoxygenation of electron beam melting polysilicon and continuous casting, comprises body of heater, is provided with electron beam melting assembly and continuous casting assembly in body of heater 1, wherein:
Electron beam melting assembly comprises the smelting pot 2 of the water-cooled that is installed on body of heater internal upper part, on this smelting pot, offer spill melting pond (not pointing out in accompanying drawing), this smelting pot one side is provided with water-cooled transport tape 12, this water-cooled transport tape one side is concordant with smelting pot side mouth, opposite side is downward-sloping and be provided with flow-guiding mouth 13, on water-cooled transport tape, have Baltimore groove, for by the polysilicon liquid guiding of the preliminary deoxygenation of melting, the direction to ingot casting device flows, and enter in ingot casting device by the flow-guiding mouth on water-cooled transport tape, on the body of heater of smelting pot top, be installed with electron beam gun 3 for melting, this used in electron gun is in the preliminary impurity oxygen of removing wherein of the more much higher crystal silicon material of melting oxygen level, on the body of heater of water-cooled transport tape top, be installed with electron beam gun 4 for radiation, be positioned on a wing furnace body wall of smelting pot and be provided with feeding device 5, the discharge port of this feeding device is positioned at the top of smelting pot.
Melting is removed impurity with electron beam gun for melting polysilicon material, after for some time, silicon liquid flows into the Baltimore groove of water-cooled transport tape, this Baltimore groove surface-area is larger, silicon liquid is conducive to rapid impurity removal after tiling on it, the moulding of water-cooled transport tape monomer, smelting pot and water-cooled transport tape are made by copper product, wherein pass into recirculated cooling water, to avoid fusing and to damage, water-cooled transport tape is downward-sloping, angle of inclination between itself and horizontal plane is 5 °, so that silicon liquid flows downward smoothly along Baltimore groove on water-cooled transport tape, and enter in the quartz crucible in ingot casting device by flow-guiding mouth.
Continuous casting assembly comprises the turning axle 11 that is installed on bottom of furnace body, between turning axle and bottom of furnace body, by dynamic seal, be connected, to guarantee the stopping property of body of heater, and can realize the at the uniform velocity rotation of circumference of level, circumferential motion rate-controlling is at 10mm/s-50mm/s, rotation platform 10 is fixedly installed on turning axle, can horizontally rotate around turning axle, on rotation platform, circle distribution formula is provided with ingot casting device, angle between every two ingot casting devices equates, ingot casting device is positioned at water-cooled transport tape below, and within the vertical axis of the flow-guiding mouth position of water-cooled transport tape is positioned at the movement locus scope of ingot casting device, to guarantee that the silicon liquid flowing out from flow-guiding mouth adds the quartz crucible of ingot casting device smoothly.
Ingot casting device is 6, circle distribution formula is fixedly installed on rotation platform, angle between every two ingot casting devices is 60 °, ingot casting device comprises the magnetism servo-electric motor water-cooling being fixedly installed on rotation platform, this magnetism servo-electric motor water-cooling is provided with quartz crucible, is provided with from inside to outside well heater and insulation sleeve on quartz crucible outer wall, and magnetism servo-electric motor water-cooling can adopt water-cooled ingot pulling mechanism, the graphite heater that the well heater now adopting is integrated, is kept liquid and is drawn ingot to realize directional long crystal technique by heating; Also can adopt fixing magnetism servo-electric motor water-cooling, the graphite heater that the well heater now adopting is split, this graphite heater is divided into three of upper, middle and lower graphite heating sheet, by regulating the heating power of the graphite heating sheet of upper, middle and lower to carry out directional long crystal technique, this ingot casting device can be realized all processes of directional long crystal casting ingot process.
Embodiment 2:
Device described in employing embodiment 1, carries out the deoxygenation of electron beam melting polysilicon and continuous casting technique,
Concrete steps are as follows:
(1) charging vacuumizes: by granular size, be to put into feeding device after the polycrystalline silicon material cleaning, drying that 10-12mm, purity are 99.996%, oxygen level is 20ppmw, the polycrystalline silicon ingot casting bed material of 6N is laid in quartz crucible bottom at ingot casting device, and the vacuum tightness of body of heater is evacuated to 3 * 10
-2pa, the vacuum tightness of electron beam gun is evacuated to 4 * 10
-3pa, pre-thermionic electron guns 15min;
(2) preliminary deoxygenation: add continuously the polycrystalline silicon material in step (1) by feeding device in electron beam melting furnace smelting pot, start melting electron beam gun, setting melting is 1200mA fusing the preliminary impurity oxygen of removing wherein of melting 15min polycrystalline silicon material with the electron beam line of electron beam gun;
(3) further deoxygenation: the polysilicon liquid after preliminary deoxygenation enters water-cooled transport tape and in the liquid further deoxygenation of maintenance under electron beam gun effect for radiation, obtains the polysilicon liquid after deoxygenation, and setting radiation in this process is 800mA with the electron beam line of electron beam gun;
(4) polycrystalline silicon casting ingot process: the 6N(massfraction that lay the quartz crucible bottom of heat fused ingot casting device is 99.9999%) polycrystalline silicon ingot casting bed material becomes liquid state, polysilicon liquid after deoxygenation is guided in the quartz crucible that enters ingot casting device by flow-guiding mouth, the heater power of controlling ingot casting device maintains this polysilicon liquid for liquid, in the quartz crucible of ingot casting device, add this polysilicon liquid continuously, to reach quartz crucible volume 80% after, by rotation platform, rotate and the rotation of this ingot casting device is left and carried out directional long crystal casting ingot process, in this process, control directional long crystal speed and be 1.2cm-1.3cm/h (centimetre per hour), another ingot casting device turns to water-cooled transport tape flow-guiding mouth below simultaneously,
(5) continuous casting: repeat the operation in step (2), (3) and (4), polysilicon liquid after deoxygenation in last ingot casting device quartz crucible reach its volume 80% time, stop electron beam melting, until directional long crystal casting ingot process in all ingot casting devices, after completing, take out polycrystalline silicon ingot casting, obtain the polycrystalline silicon ingot casting of electron beam deoxygenation, this polycrystalline silicon ingot casting detects through second ion mass spectroscopy (SIMS), its oxygen level is lower than second ion mass spectroscopy limit of detection, lower than 0.0571ppmw.
Embodiment 3:
Device described in employing embodiment 1, carries out the deoxygenation of electron beam melting polysilicon and continuous casting technique,
Concrete steps are as follows:
(1) charging vacuumizes: by granular size, be to put into feeding device after the polycrystalline silicon material cleaning, drying that 24-30mm, purity are 99.997%, oxygen level is 11ppmw, the polycrystalline silicon ingot casting bed material of 6N is laid in quartz crucible bottom at ingot casting device, and the vacuum tightness of body of heater is evacuated to 4 * 10
-2pa, the vacuum tightness of electron beam gun is evacuated to 4.5 * 10
-3pa, pre-thermionic electron guns 13min;
(2) preliminary deoxygenation: add continuously the polycrystalline silicon material in step (1) by feeding device in electron beam melting furnace smelting pot, start melting electron beam gun, setting melting is 800mA fusing the preliminary impurity oxygen of removing wherein of melting 5min polycrystalline silicon material with the electron beam line of electron beam gun;
(3) further deoxygenation: the polysilicon liquid after preliminary deoxygenation enters water-cooled transport tape and in the liquid further deoxygenation of maintenance under electron beam gun effect for radiation, obtains the polysilicon liquid after deoxygenation, and setting radiation in this process is 500mA with the electron beam line of electron beam gun;
(4) polycrystalline silicon casting ingot process: the 6N polycrystalline silicon ingot casting bed material that lay the quartz crucible bottom of heat fused ingot casting device is liquid, polysilicon liquid after deoxygenation guides in the quartz crucible that enters ingot casting device by flow-guiding mouth, the heater power of controlling ingot casting device maintains this polysilicon liquid for liquid, in the quartz crucible of ingot casting device, add this polysilicon liquid continuously, to reach quartz crucible volume 82% after, by rotation platform, rotate and the rotation of this ingot casting device is left and carried out directional long crystal casting ingot process, in this process, control directional long crystal speed and be 1.2cm-1.3cm/h (centimetre per hour), another ingot casting device turns to water-cooled transport tape flow-guiding mouth below simultaneously,
(5) continuous casting: repeat the operation in step (2), (3) and (4), polysilicon liquid after deoxygenation in last ingot casting device quartz crucible reach its volume 82% time, stop electron beam melting, until directional long crystal casting ingot process in all ingot casting devices, after completing, take out polycrystalline silicon ingot casting, obtain the polycrystalline silicon ingot casting of electron beam deoxygenation, this polycrystalline silicon ingot casting detects through second ion mass spectroscopy (SIMS), its oxygen level is lower than second ion mass spectroscopy limit of detection, lower than 0.0571ppmw.
Device described in employing embodiment 1, carries out the deoxygenation of electron beam melting polysilicon and continuous casting technique,
Concrete steps are as follows:
(1) charging vacuumizes: by granular size, be to put into feeding device after the polycrystalline silicon material cleaning, drying that 15-20mm, purity are 99.998%, oxygen level is 4ppmw, the polycrystalline silicon ingot casting bed material of 6N is laid in quartz crucible bottom at ingot casting device, and the vacuum tightness of body of heater is evacuated to 4.5 * 10
-2pa, the vacuum tightness of electron beam gun is evacuated to 4.7 * 10
-3pa, pre-thermionic electron guns 10min;
(2) preliminary deoxygenation: add continuously the polycrystalline silicon material in step (1) by feeding device in electron beam melting furnace smelting pot, start melting electron beam gun, setting melting is 200mA fusing the preliminary impurity oxygen of removing wherein of melting 20min polycrystalline silicon material with the electron beam line of electron beam gun;
(3) further deoxygenation: the polysilicon liquid after preliminary deoxygenation enters water-cooled transport tape and in the liquid further deoxygenation of maintenance under electron beam gun effect for radiation, obtains the polysilicon liquid after deoxygenation, and setting radiation in this process is 200mA with the electron beam line of electron beam gun;
(4) polycrystalline silicon casting ingot process: the 6N polycrystalline silicon ingot casting bed material that lay the quartz crucible bottom of heat fused ingot casting device, polysilicon liquid after deoxygenation guides in the quartz crucible that enters ingot casting device by flow-guiding mouth, the heater power of controlling ingot casting device maintains this polysilicon liquid for liquid, in the quartz crucible of ingot casting device, add this polysilicon liquid continuously, to reach quartz crucible volume 85% after, by rotation platform, rotate and the rotation of this ingot casting device is left and carried out directional freeze casting ingot process, in this process, control directional long crystal speed and be 1.2cm-1.3cm/h (centimetre per hour), another ingot casting device turns to water-cooled transport tape flow-guiding mouth below simultaneously,
(5) continuous casting: repeat the operation in step (2), (3) and (4), polysilicon liquid after deoxygenation in last ingot casting device quartz crucible reach its volume 85% time, stop electron beam melting, until directional freeze casting ingot process in all ingot casting devices, after completing, take out polycrystalline silicon ingot casting, obtain the polycrystalline silicon ingot casting of electron beam deoxygenation, this polycrystalline silicon ingot casting detects through second ion mass spectroscopy (SIMS), its oxygen level is lower than second ion mass spectroscopy limit of detection, lower than 0.0571ppmw.
Claims (10)
1. a method for the deoxygenation of electron beam melting polysilicon and continuous casting, is characterized in that: first body of heater and electron beam gun are vacuumized to pre-thermionic electron guns; Then by feeding device, in electron beam melting furnace smelting pot, add continuously polycrystalline silicon material, start melting, with electron beam gun, polycrystalline silicon material is carried out to electron beam melting, impurity oxygen is tentatively removed in melting; Polysilicon liquid after preliminary deoxygenation enters water-cooled transport tape and in the liquid further deoxygenation of maintenance under electron beam gun effect for radiation, obtains the polysilicon liquid after deoxygenation; Finally the polysilicon liquid after deoxygenation is guided and entered in ingot casting device by flow-guiding mouth, carry out directional long crystal casting ingot process, obtain polycrystalline silicon ingot casting, after an ingot casting device directional long crystal casting ingot process completes, by rotating rotation platform, make another ingot casting device being mounted thereon be positioned at flow-guiding mouth below, proceed directional long crystal casting ingot process, extremely in all ingot casting devices, directional long crystal casting ingot process completes.
2. the method for a kind of electron beam melting polysilicon according to claim 1 deoxygenation and continuous casting, is characterized in that concrete steps are as follows:
(1) charging vacuumizes: after the polycrystalline silicon material cleaning, drying that is 10-30mm by granular size, put into feeding device, in the quartz crucible bottom of ingot casting device, lay the polycrystalline silicon ingot casting bed material of 6N, and body of heater and electron beam gun are vacuumized to pre-thermionic electron guns 10-15min;
(2) preliminary deoxygenation: add continuously the polycrystalline silicon material in step (1) by feeding device in electron beam melting furnace smelting pot, start melting electron beam gun, setting melting is 200-1200mA fusing the preliminary impurity oxygen of removing wherein of melting polysilicon material with the electron beam line of electron beam gun;
(3) further deoxygenation: the polysilicon liquid after preliminary deoxygenation enters water-cooled transport tape and the liquid further deoxygenation of maintenance under electron beam gun effect for radiation, obtain the polysilicon liquid after deoxygenation, in this process, setting radiation is 200-800mA with the electron beam line of electron beam gun;
(4) polycrystalline silicon casting ingot process: the 6N polycrystalline silicon ingot casting bed material that lay the quartz crucible bottom of heat fused ingot casting device, polysilicon liquid after deoxygenation is guided in the quartz crucible that enters ingot casting device by flow-guiding mouth, the heater power of controlling ingot casting device maintains polysilicon for liquid, in the quartz crucible of ingot casting device, add this polysilicon liquid continuously, to reaching after the 80%-85% of quartz crucible volume, by rotation platform, rotate and the rotation of this ingot casting device is left and carried out directional long crystal casting ingot process, another ingot casting device turns to the flow-guiding mouth below of water-cooled transport tape simultaneously,
(5) continuous casting: repeat the operation in step (2), (3) and (4), when the polysilicon liquid after deoxygenation in last ingot casting device quartz crucible reaches the 80%-85% of its volume, stop electron beam melting, until directional long crystal casting ingot process in all ingot casting devices, after completing, take out polycrystalline silicon ingot casting, obtain the polycrystalline silicon ingot casting of electron beam deoxygenation.
3. according to the arbitrary described a kind of electron beam melting polysilicon deoxygenation of claim 1 or 2 and the method for continuous casting, it is characterized in that: the low vacuum of described body of heater is in 5 * 10
-2pa, the low vacuum of described electron beam gun is in 5 * 10
-3pa.
4. according to the arbitrary described a kind of electron beam melting polysilicon deoxygenation of claim 1 or 2 and the method for continuous casting, it is characterized in that: described polycrystalline silicon material purity is 99.996%-99.998%, oxygen level is 4-20ppmw.
5. the method for a kind of electron beam melting polysilicon according to claim 2 deoxygenation and continuous casting, is characterized in that: in described step (2), the smelting time of melting polysilicon material removal impurity oxygen is wherein 5-20min.
6. an equipment for electron beam melting polysilicon according to claim 1 deoxygenation and continuous casting, comprises body of heater, it is characterized in that: in body of heater, be provided with electron beam melting assembly and continuous casting assembly, wherein:
Electron beam melting assembly comprises the smelting pot of the water-cooled that is installed on body of heater internal upper part, on this smelting pot, offer spill melting pond, this smelting pot one side is provided with water-cooled transport tape, this water-cooled transport tape one side is concordant with smelting pot side mouth, opposite side is downward-sloping and be provided with flow-guiding mouth, on the body of heater of smelting pot top, be installed with melting electron beam gun, on the body of heater of water-cooled transport tape top, be installed with radiation electron beam gun, be positioned on a wing furnace body wall of smelting pot and be provided with feeding device, the discharge port of this feeding device is positioned at the top of smelting pot;
Continuous casting assembly comprises the turning axle that is installed on bottom of furnace body, rotation platform is fixedly installed on turning axle, and horizontally rotate around turning axle, on rotation platform, circle distribution formula is provided with ingot casting device, ingot casting device is positioned at water-cooled transport tape below, and within the vertical axis of the flow-guiding mouth position of water-cooled transport tape is positioned at the movement locus scope of ingot casting device.
7. the equipment of a kind of electron beam melting polysilicon according to claim 6 deoxygenation and continuous casting, is characterized in that: described water-cooled transport tape is downward-sloping, and the angle of inclination between itself and horizontal plane is 5 °～15 °.
8. according to the arbitrary described a kind of electron beam melting polysilicon deoxygenation of claim 6 or 7 and the equipment of continuous casting, it is characterized in that: described water-cooled transport tape monomer moulding or with smelting pot global formation.
9. the equipment of a kind of electron beam melting polysilicon according to claim 6 deoxygenation and continuous casting, is characterized in that: described ingot casting device is 3-6 platform, is fixedly installed on rotation platform.
10. according to the arbitrary described a kind of electron beam melting polysilicon deoxygenation of claim 6 or 9 and the equipment of continuous casting, it is characterized in that: described ingot casting device comprises the magnetism servo-electric motor water-cooling being fixedly installed on rotation platform, this magnetism servo-electric motor water-cooling is provided with quartz crucible, is provided with from inside to outside well heater and insulation sleeve on quartz crucible outer wall.
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| CN201310598300.XA CN103741210B (en) | 2013-11-22 | 2013-11-22 | A kind of electronic torch melting polysilicon deoxygenation and the method and apparatus of continuous casting |
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