CN101565852B - Crystal continuous producing device and method for continuously producing polysilicon by using same - Google Patents
Crystal continuous producing device and method for continuously producing polysilicon by using same Download PDFInfo
- Publication number
- CN101565852B CN101565852B CN2008100892446A CN200810089244A CN101565852B CN 101565852 B CN101565852 B CN 101565852B CN 2008100892446 A CN2008100892446 A CN 2008100892446A CN 200810089244 A CN200810089244 A CN 200810089244A CN 101565852 B CN101565852 B CN 101565852B
- Authority
- CN
- China
- Prior art keywords
- crystalline forming
- crystalline
- deflector roll
- polysilicon
- forming device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a crystal continuous producing device which comprises a melting device and a plurality of crystallizing forming devices, wherein the melting device is provided with a feeding hole and a discharging hole, and the crystallizing forming devices are sequentially arranged. A crystallizing forming device on the end part in the crystallizing forming devices which are sequentially arranged is used for receiving the liquid in a melting state from the discharging hole, and enables the liquid in a melting state to be cooled and crystallized. The crystallizing forming devices sequentially arranged behind the crystallizing forming device of the end part are used for enabling the crystal from the crystallizing forming device of the end part to continuously grow and form zoned crystal. The invention also provides a continuous producing method of polysilicon. The crystal continuous producing device of the invention can continuously produce crystal, and particularly, the polycrystal prepared by the crystal continuous producing device and the polysilicon continuous producing method of the invention can be used for preparing a polysilicon solar battery.
Description
Technical field
The method that the present invention relates to a kind of crystal continuous production unit and use this equipment continuous production polysilicon.
Background technology
Advantages such as sun power is widely distributed with it, cleanliness without any pollution become the first-selected energy that solves energy dilemma and environmental degradation, so the research of high-efficiency and low-cost solar cell enjoys common people to pay close attention to.Wherein polysilicon solar cell because of photoelectric transformation efficiency up to 20.3% and the focus that forms industry research with low cost, carry out just in high gear about the research of solar-grade polysilicon.
US 6090361 discloses a kind of preparation method of solar cell purifying silicon, this method comprises reduction with carbon fused silicon oxide, obtain metallurgical grade silicon, then the fused metallurgical grade silicon is poured into and carried out directional freeze is lower than 1000ppm with preparation Al and Fe content solid silicon in the mould, then this solid silicon is carried out vacuum fusion to remove dephosphorization, carry out refining subsequently to remove carbon and boron wherein, solidify then and the refining of purification gained after molten silicon, describedly be solidified as single curing schedule.
CN 1803598A discloses a kind of method for preparing solar-grade polysilicon, and this method comprises carries out metallurgical grade silicon after the vacuum refinement melt to be carried out the directional freeze processing, and it is 10 that described directional freeze is handled in vacuum tightness
-2-10
-5Handkerchief, melt temperature are to carry out in 1430-1500 ℃ the induction vacuum oven, and speed of cooling is the 0.1-2 mm/min, treat that stove is cooled to condensed silicon to be carried out crop after the room temperature and handle, and obtain solar-grade polysilicon and silicon alloy.
The common feature of aforesaid method is that directional freeze is carried out in crucible, and prepared polysilicon is the ingot shape, and the size of silicon ingot depends on the size of crucible, can not carry out serialization production.And the silicon ingot of producing must be prepared into sheet through cutting and just can be used on the solar cell, so both increased follow-up cutting technique, caused the material cutting loss of polysilicon again, cause the cost of gained solar-grade polysilicon to increase indirectly, become the yoke that photovoltaic industry continues extensive development.
In addition, the material of existing other ingot casting crystalline growth, for example CaF
2, LiNbO
3, SiC etc. crystallization also in the container of bottoms such as crucible sealing, carry out substantially, therefore, existing crystallization operation can not carry out continuously, can not carry out the industrialization continuous production.
Summary of the invention
Particularly the preparation method of solar-grade polysilicon can not the quantity-produced shortcoming to the objective of the invention is to overcome crystal in the prior art, provide a kind of can the continuous production crystal particularly the continuous production equipment of solar-grade polysilicon and the method for using this equipment continuous production polysilicon.
The invention provides a kind of crystal continuous production unit, this continuous production equipment comprises melting plant, described melting plant has opening for feed and discharge port, it is characterized in that, this continuous production equipment also comprises a plurality of crystalline forming devices and cutting part, a plurality of crystalline forming devices are arranged in order and have successively a temperature that descends, a crystalline forming device of a plurality of crystalline forming device medial end portions that are arranged in order is used to receive the liquid from the molten state of discharge port, and make the liquid cooling and the crystallization of molten state, being sequentially arranged in crystalline forming device after the crystalline forming device of described end, to be used to make crystal from the crystalline forming device of described end to continue crystalline forming be zoned crystal; Described cutting part be used to cut from the zoned crystal of the crystalline forming device of described end opposing ends portion.
The present invention also provides a kind of continuous producing method of polysilicon, it is characterized in that, this method comprises the solid state si heating and melting, make silicon after the fusion successively by a plurality of crystalline formings district then, the temperature in described a plurality of crystalline formings district descends successively, a crystalline forming district of a plurality of crystalline formings district medial end portions is used to receive the silicon of molten state, and the silicon of molten state is cooled off and crystallization, being arranged in crystalline forming district after the crystalline forming district of described end, to be used to make crystal from the crystalline forming district of described end to continue crystalline forming be banded polysilicon, and this method also comprises cuts described banded polysilicon.Crystal continuous production unit of the present invention can the continuous production crystal, particularly use crystal continuous production unit of the present invention, adopt the better crystallinity degree of the polysilicon of polysilicon continuous production method preparation of the present invention, the resistivity of polysilicon chip is higher, be the 0.98-1.27 ohmcm, and the general commercially available polysilicon chip resistivity that is is the 0.5-3 ohmcm, and the photoelectric conversion rate with the polysilicon solar cell of this polysilicon preparation is higher, be 14.6-17.8%, the photoelectric conversion rate of commercially available polysilicon solar cell is generally 13-15.5%, has illustrated that the polysilicon of the present invention's preparation can be used for preparing polysilicon solar cell; In addition, crystal continuous production unit of the present invention not only can the continuous production polysilicon, and compare with the existing device of producing polysilicon, the polysilicon that the present invention produces is owing to can be banded, therefore only need this zonal polysilicon is got final product according to the required size cutting of solar cell, compare with the ingot shape polysilicon that prior art is produced, simplified cutting step and the requirement that has reduced cutting unit, so production cost is lower.
Description of drawings
Fig. 1 is the crystal continuous production unit synoptic diagram of preferred implementation of the present invention.
Embodiment
The invention provides a kind of crystal continuous production unit, this continuous production equipment comprises melting plant, described melting plant has opening for feed and discharge port, wherein, this continuous production equipment also comprises a plurality of crystalline forming devices, a plurality of crystalline forming devices are arranged in order, a crystalline forming device of a plurality of crystalline forming device medial end portions that are arranged in order is used to receive the liquid from the molten state of discharge port, and make the liquid cooling and the crystallization of molten state, be sequentially arranged in crystalline forming device after the crystalline forming device of described end and be used to make from the crystal continued growth of the crystalline forming device of described end and be shaped to zoned crystal.
The present invention has no particular limits the material and the shape of described melting plant, as long as can make solid state si be molten state in melting plant and do not react with silicon.For example, described melting plant can comprise container and well heater of a dress solid state si, and described well heater is positioned at the outside of described container, is used to make the solid matter in the container to reach molten state; The container of the Any shape that described container can be made for any material that does not react with silicon for example can be columniform quartz crucible, for the purity that the silicon oxide that prevents quartz crucible enters the polysilicon of influence preparation in the solid state si, preferred built-in Si
3N
4The quartz crucible of layer.For the crystalline forming device of the end of the discharge port that makes described melting plant and next-door neighbour's discharge port is communicated with better, preferably the discharge port of melting plant is designed to taper shape as shown in Figure 1.Described well heater can be induction heater or graphite heater etc.Melting plant with this structure can be commercially available, for example can be for being 12 inches high-purity quartz crucibles to brilliant imperial institutional purchase upper end, Hebei, then the bottom of this quartz crucible is removed, become penetrating quartz crucible up and down, the actual time spent can require producer that quartz crucible is made penetrating shape up and down.
Further under the preferable case, the opening for feed of melting plant or discharge port place are provided with metering valve, are used to control the amount of substance that enters melting plant or crystalline forming device.
On principle, as long as being positioned at the temperature of the crystalline forming device after the crystalline forming device of end is lower than crystal and is in the required temperature of molten state and can realizes purpose of the present invention, there is no particular limitation and to the number of crystalline forming device, yet the crystalline forming device is many more, the temperature that is each crystalline forming district differs more little, the crystalline effect is good more, but the crystalline forming device is many more, correspondingly cost is high more, therefore, the device of crystalline forming described in the present invention is at least 2, is preferably 3-15, more preferably 3-10.
Described crystalline forming device can be various device or the parts that can realize crystalline forming.Under the preferable case, among the present invention, each crystalline forming device comprises that a deflector roll is right, and this deflector roll is to comprising two deflector rolls positioned opposite to each other.Adopt the crystalline forming device of deflector roll form, can improve the surface finish of crystal product on the one hand by the roll-in of deflector roll, the roll-in by deflector roll can also realize moving continuously of crystal product on the other hand.Described deflector roll can be known various deflector roll, generally comprises roller part and roll shaft part, and the roller part can partly be done circumference around roll shaft and rotate.There is no particular limitation to the axial length of described deflector roll, as long as be not less than the width of the crystal product of required production.Usually, when the crystal continuous production unit is used to produce the polysilicon that is used for solar cell, because the width of required polysilicon is generally 125 millimeters, 156 millimeters or 210 millimeters in the solar cell, therefore the axial length of described deflector roll can be 10-50 centimetre, more preferably the integral multiple of the width of required polysilicon.
Shortest distance between the described deflector roll face positioned opposite to each other can equate or not wait, preferred equating, can improve the crystalline planeness like this, shortest distance between the described deflector roll face positioned opposite to each other generally depends on the thickness of the crystal product that will produce, the thickness of the crystal product of producing is big more, and the shortest distance between the deflector roll face then positioned opposite to each other is also big more.Normal conditions, when the crystal continuous production unit is used to produce the polysilicon that is used for solar cell, because the thickness of required polysilicon is generally 220 microns, 240 microns, 270 microns or 300 microns in the solar cell, therefore the shortest distance between the described deflector roll face positioned opposite to each other is preferably the 200-300 micron, thereby make that the thickness of the crystal product behind the crystallisation by cooling is the 200-300 micron, the shortest distance between the deflector roll face more preferably positioned opposite to each other is the integral multiple of the thickness of required polysilicon.
The present invention to described each deflector roll between set-up mode there is no particular limitation, can determine according to required crystal product shape, during the preparation polysilicon, under the preferable case, described each deflector roll between set-up mode make a plurality of deflector rolls between the space that forms be band shape or strip, the polysilicon product of Sheng Chaning is banded polysilicon like this.Further under the preferable case, the right center wire of each deflector roll is parallel to each other, and the mid point of line segment at center that connects two right deflector rolls of each deflector roll can further improve the planeness of zoned crystal product like this on same straight line.In addition, preferred described straight line is perpendicular to the ground, helps the zoned crystal product like this and moves under action of gravity, helps the continuous production of zoned crystal product.
In addition, the shortest distance between two deflector rolls of the right the same side of adjacent two deflector rolls is preferably 5-15 centimetre.Thermograde in the time of can guaranteeing to prepare crystal so on the one hand is better, and the opposing party can guarantee that the face roll-in is relatively continuous.
Further under the preferable case, when each described crystalline forming device comprise a deflector roll to the time, this equipment can also comprise guide arrangement, described guide arrangement the deflector roll of melting plant and end between, the deflector roll centering that is used to guide the liquid of the molten state that comes from discharge port to enter described end.The present invention has no particular limits the shape and the size of described guide arrangement, as long as can play the liquid effusive effect outside the crystalline forming device of described end that prevents molten state.For example, described guide arrangement is to be arranged between two deflector rolls of deflector roll centering of described end and along two baffle plates that axially are spaced apart from each other of deflector roll, and the distance between two baffle plates is the axial length of deflector roll; Perhaps described guide arrangement be positioned at melting plant discharge port the outside and be close to the cylinder of the right inboard of the deflector roll of described end.
In order to make the liquid rapid crystallization of the molten state that initially enters the crystalline forming device, under the preferable case, described crystalline forming device can also comprise quenching apparatus, described quenching apparatus can be positioned at the lower edge of the crystalline forming device of described end, when the crystalline forming device that is used for described end begins to receive from the liquid of the molten state of discharge port, make the liquid cooling and the crystallization fast of effusive molten state from the crystalline forming device of described end, crystal is slowly grown then, treat to remove quenching apparatus behind crystalchecked growth and the dimensionally stable, for different crystal, the time that removes quenching apparatus is different, for example, for polysilicon, just remove quenching apparatus in the time of generally more than polycrystalline silicon growth to 8 centimetre, and the crystal that will be longer than adjacent two crystalline forming devices cuts off so that the crystal of remainder can enter next crystalline forming device smoothly, obtains the thickness homogeneous continuously, the crystal product of surfacing.The present invention has no particular limits described quenching apparatus, as long as can make the liquid cooling and the crystallization of effusive molten state from the crystalline forming device of described end, for example can be the chilling crucible, described chilling crucible is that temperature is 30-100 ℃ a crucible, be preferably quartz crucible, crucible bottom can have the circulating water of loop to be in 30-100 ℃ to guarantee crucible, and this quartz crucible can be made a loop in flat quartz crucible bottom, and both ends open leads to water coolant.The liquid of the molten state when just beginning to produce in order to make can become crystal by rapid crystallization, reduce the disqualification rate of product, the preferred described quenching apparatus of the present invention is between two crystalline forming devices of next-door neighbour's melting plant, and the distance between the crystalline forming device of further preferred described quenching apparatus and described end is the 5-15% of the distance between above-mentioned two crystalline forming devices.
Each described crystalline forming device can also comprise temperature regulating device, be used to control the temperature of this crystalline forming device, described temperature regulating device comprises temperature control parts and heater block, described crystalline forming device is hollow or entity structure, described heater block is arranged in crystalline forming device or outer, for example, described crystalline forming device be deflector roll to the time, described heater block can lay respectively in two right deflector rolls of the deflector roll of hollow, perhaps lay respectively at the outer of two right deflector rolls of deflector roll, when described heater block lays respectively at the outer of two right deflector rolls of deflector roll, guarantee that the outer has the deflector roll of heater block to remain round pie, the preferred described heater block of the present invention is arranged in the crystalline forming device, among the present invention if no specified otherwise, described crystalline forming device is a hollow structure, and described heater block is arranged in the crystalline forming device, and described temperature control parts are electrically connected with crystalline forming device and heater block.Described heater block can be induction heater, platinum wire or platinum-rhodium wire etc., and described temperature control parts can be platinum rhodium thermocouple or infrared measurement of temperature Controlling System.The crystalline forming device that satisfies above-mentioned condition for example can be Φ 100mm and the Φ 200mm quartz-ceramics roller that sky, Xuzhou grand high-technology industry company limited produces.
Under the preferable case, crystal continuous production unit provided by the invention can also comprise cutting part, described cutting part comprises cutting tool, described cutting part is used to cut the zoned crystal from another crystalline forming device of end, be cut to required size, when for example preparing polysilicon, its size according to desired silicon chip in the solar cell can be cut into the integral multiple of desired size or desired size, for example the length of used polysilicon is generally 125 millimeters, 156 millimeters, 210 millimeters in the solar cell.
Crystal after the cutting can be transported by transmission mechanism.Under the preferable case, described cutting part can also comprise a cutting baffle plate, and described transmission mechanism is positioned at a side of cutting tool, and described cutting baffle plate is positioned at the opposite side of cutting tool, with the crystal after preventing to cut away from transmission mechanism.
For crystal is cooled off fast, under the preferable case, described cutting is carried out in the presence of the cooling fluid of cooling pool.Therefore, under the preferable case, crystal continuous production unit of the present invention can also comprise cooling pool, and described cooling pool is used to cool off the crystal that comes from described crystalline forming device, and described cutting part can be arranged in cooling pool.Wherein, the distance between the end of described cooling fluid and a plurality of crystalline forming devices can be 0.1-2 rice, is preferably 0.5-1 rice.The end of described a plurality of crystalline forming devices is meant the end away from melting plant of a plurality of crystalline forming devices.
Crystal continuous production unit of the present invention also comprises drive unit, and described drive unit can be a various forms of drive unit well known in the art, if can for the crystalline forming device for example deflector roll to stable propulsion source is provided.Described drive unit can adopt worm and gear transmission, belt transmission or geartransmission.
According to the present invention, when preparing crystal with crystal continuous production unit of the present invention, material to be crystallized opening for feed from melting plant can be added to the container of melting plant, vessel in heating fusion at melting plant, make the material a plurality of crystalline forming devices by being arranged in order successively after the fusion then, a crystalline forming device of a plurality of crystalline forming device medial end portions that are arranged in order is used to receive the liquid from the molten state of discharge port, and make the liquid cooling and the crystallization of molten state, be sequentially arranged in crystalline forming device after the crystalline forming device of described end and be used to make from the crystal continued growth of the crystalline forming device of described end and be shaped to zoned crystal.
Crystal continuous production unit of the present invention also can comprise the crystal purification devices, makes crystalline purification and crystallization carry out continuously, for example, when the preparation polysilicon, can be the raw material production polysilicon with silicon-dioxide or metallurgical grade silicon just.Described crystal purification devices can be to well known to a person skilled in the art various devices, and for example, when being used to produce solar-grade polysilicon, described crystal purification devices can be US 6090361 or the disclosed purifying plant of CN 1803598A.Under the situation that does not comprise purification devices, the used solid state si of the present invention is a solar level purity silicon, described solar level purity silicon can make with the method for routine, in order to satisfy the performance requriements that the polysilicon make is used to prepare polysilicon solar cell, the present invention preferably use purity as the solar level purity silicon of 99.999-99.9999% as solid state si.
According to of the present invention one preferred embodiment, as shown in Figure 1, crystal continuous production unit provided by the invention comprises melting plant, be positioned at a plurality of crystalline forming devices of melting plant bottom, between the deflector roll of described end two deflector rolls in to 8 and along two baffle plates 5 that axially are spaced apart from each other of deflector roll, (deflector roll that is positioned at described end one of them baffle plate 5 to an end only is shown among the figure, another baffle plate 5 along deflector roll to 8 axially be positioned at its other end), two deflector rolls of next-door neighbour's melting plant between to 8 chilling crucible (not shown) and the deflector roll of described chilling crucible and the described end distance between to 8 be the right the same side of adjacent two deflector rolls two deflector rolls between the 5-15% of shortest distance, heater block 7 in the temperature regulating device, described melting plant comprises quartz crucible 3 and well heater 4, described quartz crucible 3 comprises opening for feed a, discharge port b, described each crystalline forming device comprises that a deflector roll is to 8, described deflector roll comprises transmission shaft 6 to 8, described deflector roll can rotate under transmission shaft 6 effects 8, and described heater block 7 is arranged in the deflector roll of hollow.
Further under the preferable case, polysilicon continuous production equipment provided by the invention also comprises cutting part and cooling pool 12, and described cutting part comprises cutting tool 10 and cutting baffle plate 11, and described cutting tool and cutting baffle plate 11 are arranged in the cooling fluid of cooling pool 12.
The invention provides a kind of continuous producing method of polysilicon, wherein, this method comprises the solid state si heating and melting, make silicon after the fusion successively by a plurality of crystalline formings district then, the temperature in described a plurality of crystalline formings district descends successively, a crystalline forming district of a plurality of crystalline formings district medial end portions is used to receive the silicon of molten state, and make the silicon cooling and the crystallization of molten state, be arranged in crystalline forming district after the crystalline forming district of described end and be used to make from the crystal continued growth in the crystalline forming district of described end and be shaped to banded polysilicon.
According to the present invention, when silicon passed through the crystalline forming district of described end, the silicon after the described fusion was molten state; When silicon passed through other crystalline forming district, the silicon of described molten state was crystalline silicon.
When producing polysilicon with crystal continuous production equipment of the present invention, described crystalline forming district is corresponding with the crystalline forming device, under the preferable case, described crystalline forming district and deflector roll be to corresponding, promptly each deflector roll to and the right rolling drum surface of this deflector roll between the space be a crystalline forming district.
According to the present invention, described crystalline forming district is at least 2, is preferably 3-15, more preferably 5-10.The polysilicon cooling forming that is arranged so that in each described crystalline forming district is that thickness is the banded polysilicon of 200-300 micron, and the formation direction of banded polysilicon is perpendicular to the ground.
The present inventor finds, when the homo(io)thermism in each crystalline forming district, can guarantee the crystalline direction of growth unanimity that different time obtains in the continuous flow procedure, thereby make crystalline performance unanimity, even the resistivity at each position of crystalline is identical, therefore under the preferable case, the temperature in described each crystalline forming district is a definite value.For example, silicon generally is molten state in the time of 1430-1500 ℃, when therefore preparing polysilicon, the temperature of the silicon of molten state should be higher than 1430 ℃, for the silicon above the crystalline forming district that makes described end is in molten state always, the temperature of the crystalline forming device of preferred described end is 1430-1500 ℃.
The present inventor also finds, when the temperature head in every adjacent two crystalline forming districts was identical, the degree of crystallinity of the polysilicon of generation was better and higher by the photoelectric conversion rate of the solar cell of this polysilicon preparation.Therefore, under the preferable case, the temperature head in two adjacent crystalline forming districts is identical, and for example the temperature in each crystalline forming district can be hanged down 100-500 ℃ than the temperature in adjacent previous crystalline forming district.
Silicon after the fusion can be the 1-3 cm per minute by the speed in each crystalline forming district.The distance in adjacent two crystalline forming districts can be 5-15 centimetre.Can control the speed of silicon by each crystalline forming district after the fusion by control deflector roll right rotating speed.
This method comprises that also the silicon to the molten state that begins a crystal shaping area by described end carries out chilling, the silicon of this molten state is cooled to below 1430 ℃ and cooling and crystallization.
The present invention has no particular limits the method for chilling, as long as can make the silicon cooling and the crystallization fast of described molten state, for example, it is 30-100 ℃ chilling crucible that the method for described chilling can be provided with a temperature for the lower edge in the crystalline forming district of described end, be preferably the quartz crucible of chilling, crucible bottom can have the circulating water of loop to be in 30-100 ℃ to guarantee crucible, the silicon of molten state touches this chilling crucible and crystallisation by cooling, to be crystallizedly can remove crucible when growing into more than 8 centimetres, and the crystal that will be longer than adjacent two crystalline forming districts is cut off and is removed so that the crystal of remainder can enter next crystalline forming district.
In order to prevent that silicon is oxidized in the process of preparation polysilicon, the present invention preferably produces polysilicon under vacuum or atmosphere of inert gases, and described rare gas element can be helium and/or argon gas.
This method can also comprise cuts described polysilicon, and described cutting can be carried out under vacuum or atmosphere of inert gases, but for crystal is cooled off fast, under the preferable case, described cutting is carried out in the presence of the cooling fluid of cooling pool.The temperature of described cooling fluid can be 20-60 ℃, and described cooling fluid reacts only otherwise with polysilicon and get final product, for example can be water, preferably secondary deionized water.Described solid state si is a solar level purity silicon.
The method that adopts this crystal continuous production unit continuous production polysilicon is described below in conjunction with Fig. 1.This method comprises and joins solid state si 1 in the quartz crucible 3 of melting plant by opening for feed a, by being arranged on quartz crucible 3 described heater block 4 heating solid state si 1 on every side, obtain the silicon 2 of molten state, the temperature that is provided with heater block 7 in the middle of the discharge port b of the silicon 2 of this molten state by melting plant enters into be 1430-1500 ℃ the end a deflector roll to 8 with the deflector roll that is arranged on described end between two deflector rolls of 8 and along in the space of two baffle plates that axially are spaced apart from each other, 5 formation of deflector roll, under of the rotation of this deflector roll to 8 transmission shaft 6, the silicon 2 of molten state flows out to 8 from the deflector roll of described end, at two deflector rolls of next-door neighbour's melting plant a temperature being set between to 8 is 30-100 ℃ quartz crucible, and the deflector roll of described quartz crucible 3 and described end is the 5-15% of the shortest distance between two deflector rolls of the right the same side of adjacent two deflector rolls to the distance between 8, the silicon 2 of molten state touches that this crucible is cooled to below 1430 ℃ and crystallisation by cooling, can remove crucible when treating more than the crystal growth to 8 centimetre, and will be longer than adjacent two deflector rolls and 8 crystal be cut off and removed so that crystal can enter next deflector roll to 8, form banded polysilicon 9, under the rotary action of gravity and transmission shaft, banded polysilicon 9 ceaselessly moves down with the speed of 1-3 cm per minute, arrives the next middle of next-door neighbour end and is provided with the deflector roll of heater block 7 to 8; The deflector roll that is provided with heater block 7 with the centre of described end is the same to 8, the next middle deflector roll that is provided with heater block 7 of next-door neighbour end carries out temperature control to 8 pairs of banded polysilicons 9, make banded polysilicon 9 continue crystalline formings and banded polysilicon 9 is delivered to the deflector roll centering that is provided with heater block 7 in the middle of thereafter next, and the like, after the deflector roll that is provided with heater block 7 through last centre is to 8, obtain banded polysilicon product; Wherein, the right temperature of each deflector roll is all than low 100-500 ℃ of the right temperature of adjacent previous deflector roll, and adjacent two deflector rolls are 5-15 centimetre to the shortest distance between two deflector rolls of the same side of 8.In this process, because each deflector roll is lower to 8 temperature than a last deflector roll to 8, make the temperature of banded polysilicon 9 constantly reduce, the continuous crystallization of the silicon of banded polysilicon 9 obtains better banded polysilicon 9 products of crystal formation.
When this polysilicon continuous production equipment also comprises cutting part and cooling pool 12, this method also comprises the banded polysilicon product that obtains sent on the cutting tool 10 that is arranged in cooling pool 12 cuts, to obtain the polysilicon product of desired size, under the stopping of cutting baffle plate 11, make polysilicon product waltz through transmission mechanism and transport at last.
According to the present invention, crystal continuous production unit provided by the invention be applicable to all can by the cooling and crystalline crystalline continuous production, this specification sheets has only been done concrete description with regard to preparation method of polycrystalline silicon, those skilled in the art can be according to instruction of the present invention, use crystal continuous production unit of the present invention, according to method of the present invention, with can be by cooling the crystalline material be the crystal that feedstock production needs.
Below in conjunction with embodiment the present invention is done detailed explanation.Used drive unit all adopts belt transmission in the embodiment of the invention, all heat with induction heater, when adding heated godet roll with induction heater, induction heater as heater block 7 lays respectively at each deflector roll in two deflector rolls of 8, all control the right temperature of each deflector roll with platinum rhodium thermocouple, platinum rhodium thermocouple and deflector roll are to being electrically connected with induction heater.Described cooling fluid is a secondary deionized water.
Embodiment 1
Present embodiment is used for illustrating the method for using crystal continuous production unit continuous production polysilicon of the present invention.
Under the atmosphere of helium,, be that 99.999% solar level purity silicon (the 5N level silicon of selecting for use Tianjin sunlight Pure Silicon Metal company limited to produce) is put into built-in Si as solid state si 1 by opening for feed a with purity with as shown in Figure 1 device
3N
4In the quartz crucible of layer (purchase be 12 inches high-purity quartz crucible) 3 in the penetrating upper end up and down of the brilliant imperial group in Hebei, by being arranged on quartz crucible 3 well heater 4 heating on every side, make solid state si 1 become the silicon 2 of molten state, the silicon 2 of molten state is that (quartzy deflector roll has one deck Si in its outside to 8 for 1430 ℃ a deflector roll of end from entering into temperature after the discharge port b of quartz crucible 3 comes out
3N
4Ceramic layer, the axial length of deflector roll is 48 centimetres (Φ 200mm quartz-ceramics rollers that the grand High Seience Technology Co., Ltd. in sky, Xuzhou produces)) with two deflector rolls of the deflector roll centering that is arranged on described end between and along in the space of two baffle plates that axially are spaced apart from each other, 5 formation of deflector roll, this deflector roll to 8 rotation under, the silicon 2 of molten state flows out to 8 from the deflector roll of described end, being provided with a temperature between to 8 at two deflector rolls of next-door neighbour's melting plant is 30 ℃ quartz crucible, and the deflector roll of described quartz crucible 3 and described end to the distance between 8 be between two deflector rolls of the right the same side of adjacent two deflector rolls shortest distance 5%, crucible bottom has the water-circulating cooling device of sealing, make crucible remain on 30 ℃, the silicon 2 of molten state touches that this crucible is cooled to below 1430 ℃ and crystallisation by cooling, the crucible that removes when growing into 8 centimetres to be crystallized, and will be longer than adjacent two right crystal of deflector roll cut off and remove so that crystal can to enter next deflector roll right, form banded polysilicon 9, banded polysilicon 9 then enters 1030 ℃ deflector roll to 8 successively with the speed of 1 cm per minute, 630 ℃ deflector roll is to 8,230 ℃ deflector roll is to 8, from 230 ℃ deflector rolls the banded polysilicon 9 that comes out 8 is entered cooling in the cooling pool 12 that 60 ℃ of cooling fluids are housed, obtain the polysilicon chip A1 of 156 millimeters * 156 millimeters * 240 microns specifications by the continuous banded polysilicon 9 that forms of 10 cuttings of the cutting tool in the cooling fluid, under the stopping of cutting baffle plate 11, make polysilicon product waltz through transmission mechanism and transport at last.Wherein, right big or small identical of each deflector roll, shortest distance between the right deflector roll face of each deflector roll is 240 microns, the right center wire of each deflector roll is parallel to each other, the mid point of line segment at center that connects two right deflector rolls of each deflector roll is on same straight line, and described straight line is vertical on ground, shortest distance between two deflector rolls of the same side that adjacent two deflector rolls are right is that 15 centimetres, right end and the distance between the cooling fluid of last deflector roll are 0.5 meter, and the right linear velocity of deflector roll is 1 cm per minute.
Embodiment 2
Present embodiment is used for illustrating the method for using crystal continuous production unit continuous production polysilicon of the present invention.
Under the atmosphere of helium,, be that 99.9999% solar level purity silicon (the 6N level silicon of selecting for use Tianjin sunlight Pure Silicon Metal company limited to produce) is put into built-in Si as solid state si 1 by opening for feed a with purity with as shown in Figure 1 device
3N
4In the quartz crucible of layer (purchase be 12 inches high-purity quartz crucible) 3 in the penetrating upper end up and down of the brilliant imperial group in Hebei, by being arranged on quartz crucible 3 well heater 4 heating on every side, make solid state si 1 become the silicon 2 of molten state, the silicon 2 of molten state is that (quartzy deflector roll has one deck Si in its outside to 8 for 1470 ℃ a deflector roll of end from entering into temperature after the discharge port b of quartz crucible 3 comes out
3N
4Ceramic layer, the axial length of deflector roll is 48 centimetres (Φ 200mm quartz-ceramics rollers that the grand High Seience Technology Co., Ltd. in sky, Xuzhou produces)) with two deflector rolls of the deflector roll centering that is arranged on described end between and along in the space of two baffle plates that axially are spaced apart from each other, 5 formation of deflector roll, this deflector roll to 8 rotation under, the silicon 2 of molten state flows out to 8 from the deflector roll of described end, being provided with a temperature between to 8 at two deflector rolls of next-door neighbour's melting plant is 60 ℃ quartz crucible, and the deflector roll of described quartz crucible 3 and described end to the distance between 8 be between two deflector rolls of the right the same side of adjacent two deflector rolls shortest distance 5%, crucible bottom has the water-circulating cooling device of sealing, make crucible remain on 60 ℃, the silicon 2 of molten state touches that this crucible is cooled to below 1430 ℃ and crystallisation by cooling, the crucible that removes when growing into 10 centimetres to be crystallized, and will be longer than adjacent two right crystal of deflector roll cut off and remove so that crystal can to enter next deflector roll right, form banded polysilicon 9, banded polysilicon 9 then enters 1170 ℃ deflector roll to 8 successively with the speed of 2 cm per minute, 870 ℃ deflector roll is to 8,570 ℃ deflector roll is to 8,270 ℃ deflector roll is in 8, from 270 ℃ deflector rolls the banded polysilicon 9 that comes out 8 is entered cooling in the cooling pool 12 that 40 ℃ of cooling fluids are housed, obtain the polysilicon chip A2 of 156 millimeters * 156 millimeters * 270 microns specifications by the continuous banded polysilicon 9 that forms of 10 cuttings of the cutting tool in the cooling fluid, under the stopping of cutting baffle plate 11, make polysilicon product waltz through transmission mechanism and transport at last.Wherein, right big or small identical of each deflector roll, shortest distance between the right deflector roll face of each deflector roll is 270 microns, the right center wire of each deflector roll is parallel to each other, the mid point of line segment at center that connects two right deflector rolls of each deflector roll is on same straight line, and described straight line is vertical on ground, shortest distance between two deflector rolls of the same side that adjacent two deflector rolls are right is that 10 centimetres, right end and the distance between the cooling fluid of last deflector roll are 1 meter, and the right linear velocity of deflector roll is 2 cm per minute.
Embodiment 3
Present embodiment is used for illustrating the method for using crystal continuous production unit continuous production polysilicon of the present invention.
Under the atmosphere of helium,, be that 99.9999% solar level purity silicon (the 6N level silicon of selecting for use Tianjin sunlight Pure Silicon Metal company limited to produce) is put into built-in Si as solid state si 1 by opening for feed a with purity with as shown in Figure 1 device
3N
4In the quartz crucible of layer (purchase be 12 inches high-purity quartz crucible) 3 in the penetrating upper end up and down of the brilliant imperial group in Hebei customization, by being arranged on quartz crucible 3 well heater 4 heating on every side, make solid state si 1 become the silicon 2 of molten state, the silicon 2 of molten state is that (quartzy deflector roll has one deck Si in its outside to 8 for 1500 ℃ a deflector roll of end from entering into temperature after the discharge port b of quartz crucible 3 comes out
3N
4Ceramic layer, the axial length of deflector roll is 48 centimetres (Φ 200mm quartz-ceramics rollers that the grand High Seience Technology Co., Ltd. in sky, Xuzhou produces)) with two deflector rolls of the deflector roll centering that is arranged on described end between and along in the space of two baffle plates that axially are spaced apart from each other, 5 formation of deflector roll, this deflector roll to 8 rotation under, the silicon 2 of molten state flows out to 8 from the deflector roll of described end, being provided with a temperature between to 8 at two deflector rolls of next-door neighbour's melting plant is 100 ℃ quartz crucible, and the deflector roll of described quartz crucible 3 and described end to the distance between 8 be between two deflector rolls of the right the same side of adjacent two deflector rolls shortest distance 5%, crucible bottom has the water-circulating cooling device of sealing, make crucible remain on 100 ℃, the silicon 2 of molten state touches that this crucible is cooled to below 1430 ℃ and crystallisation by cooling, the crucible that removes when growing into 10 centimetres to be crystallized, and will be longer than adjacent two right crystal of deflector roll cut off and remove so that crystal can to enter next deflector roll right, form banded polysilicon 9, banded polysilicon 9 then enters 1400 ℃ deflector roll to 8 successively with the speed of 3 cm per minute, 1300 ℃ deflector roll is to 8,1200 ℃ deflector roll is to 8,1100 ℃ deflector roll is to 8,1000 ℃ deflector roll is to 8,900 ℃ deflector roll is to 8,700 ℃ deflector roll is to 8,500 ℃ deflector roll is to 8,200 ℃ deflector roll is in 8, from 200 ℃ deflector rolls the banded polysilicon 9 that comes out 8 is entered cooling in the cooling pool 12 that 20 ℃ of cooling fluids are housed, obtain the polysilicon chip A3 of 156 millimeters * 156 millimeters * 300 microns specifications by the continuous banded polysilicon 9 that forms of 10 cuttings of the cutting tool in the cooling fluid, under the stopping of cutting baffle plate 11, make polysilicon product waltz through transmission mechanism and transport at last.Wherein, right big or small identical of each deflector roll, shortest distance between the right deflector roll face of each deflector roll is 300 microns, the right center wire of each deflector roll is parallel to each other, the mid point of line segment at center that connects two right deflector rolls of each deflector roll is on same straight line, and described straight line is vertical on ground, shortest distance between two deflector rolls of the same side that adjacent two deflector rolls are right is that 5 centimetres, right end and the distance between the cooling fluid of last deflector roll are 0.7 meter, and the right linear velocity of deflector roll is 3 cm per minute.
Embodiment 4-6
This embodiment is used to illustrate the performance of polysilicon provided by the invention.
(1) purity of polysilicon and resistivity measurement
In order to descend method purity and the resistivity of the polysilicon chip A1-A3 of test implementation example 1-3 preparation respectively.
Recording its purity respectively with the thermoelectric IRIS inductively coupled plasma atomic emission of the U.S. (ICP-AES) is 99.9997%, 99.99994%, 99.99993%, illustrate that the process for preparing polysilicon do not introduce other pollutent; The resistivity that records polysilicon chip respectively with the large photoelectronic SDY-4 type four point probe tester in Shanghai is respectively 0.98 ohmcm, 1.27 ohmcms, 1.24 ohmcms, and commercially available being used to prepares the resistivity of the polysilicon of solar cell and is generally the 0.5-3 ohmcm, illustrated that the polysilicon of method preparation of the present invention can be used for preparing solar cell.
(2) test of the photoelectric conversion rate of the solar cell of polysilicon preparation
Make the polysilicon chip A1-A3 that respectively embodiment 1-3 is prepared with the following method be prepared into solar cell B1-B3.
What adopt is that the silk-screen printing technique that at present most of in the world crystal silicon solar energy battery manufacturer adopts is prepared into solar cell respectively with the polysilicon that the foregoing description 1-3 makes, and mainly may further comprise the steps: will remove surperficial mechanical damage layer and make surperficial matteization through alkali lye through the polysilicon chip after the DIFFUSION TREATMENT.Adopt phosphorus oxychloride gas as diffuse source, spread in 850 ℃ horizontal silica tube, using plasma edge corrosion method is removed the P diffusion layer of periphery surface then; Remove the phosphorosilicate glass of surface diffusion layer with chemical process and (mix P
2O
5SiO
2) layer; Using plasma strengthens chemical vapour deposition at surface deposition one deck (SiN
x) antireflective coating, by positive back face printing silver slurry and the aluminium paste of silk screen print method, make surface metalation form the positive and negative electrode lead-in wire again with preparation at solar cell, pass through low-temperature bake, high temperature sintering again, make solar cell.
Adopt the photoelectric transformation efficiency of ASB-XE-175 type solar cell I-V test system and test solar cell B1-B3 to be respectively 14.6%, 16.5%, 17.8%, and the photoelectric conversion rate of commercially available polysilicon solar cell is generally 13-15.5%, has illustrated that the polysilicon of method preparation of the present invention can be used for preparing solar cell.
Claims (22)
1. crystal continuous production unit, this equipment comprises melting plant, described melting plant has opening for feed and discharge port, it is characterized in that, this equipment also comprises a plurality of crystalline forming devices and cutting part, a plurality of crystalline forming devices are arranged in order and have successively a temperature that descends, a crystalline forming device of a plurality of crystalline forming device medial end portions that are arranged in order is used to receive the liquid from the molten state of discharge port, and make the liquid cooling and the crystallization of molten state, being sequentially arranged in crystalline forming device after the crystalline forming device of described end, to be used to make crystal from the crystalline forming device of described end to continue crystalline forming be zoned crystal; Described cutting part be used to cut from the zoned crystal of the crystalline forming device of described end opposing ends portion.
2. equipment according to claim 1, wherein, described crystalline forming device is 3-15, and each crystalline forming device comprises that a deflector roll is right, and this deflector roll is to comprising two deflector rolls positioned opposite to each other.
3. equipment according to claim 2, wherein, the shortest distance between the deflector roll face positioned opposite to each other is the 200-300 micron.
4. equipment according to claim 2, wherein, the right center wire of each deflector roll is parallel to each other, and the mid point of line segment at center that connects two right deflector rolls of each deflector roll is on same straight line.
5. equipment according to claim 4, wherein, described straight line is perpendicular to the ground.
6. equipment according to claim 4, wherein, the shortest distance between two deflector rolls of the same side that adjacent two deflector rolls are right is 5-15 centimetre.
7. equipment according to claim 2, wherein, this equipment also comprises guide arrangement, described guide arrangement the deflector roll of melting plant and end between, the deflector roll centering that is used to guide the liquid of the molten state that comes from discharge port to enter described end.
8. equipment according to claim 7, wherein, described guide arrangement is to be arranged between two deflector rolls of deflector roll centering of described end and along two baffle plates that axially are spaced apart from each other of deflector roll, the distance between two baffle plates is the axial length of deflector roll; Perhaps described guide arrangement be positioned at melting plant discharge port the outside and be close to the cylinder of the right inboard of the deflector roll of described end.
9. equipment according to claim 1 and 2, wherein, described crystalline forming device also comprises quenching apparatus, described quenching apparatus is positioned at the lower edge of the crystalline forming device of described end, when the crystalline forming device that is used for described end begins to receive from the liquid of the molten state of discharge port, make the liquid cooling and the crystallization of effusive molten state from the crystalline forming device of described end.
10. equipment according to claim 9, wherein, described quenching apparatus is the chilling crucible.
11. equipment according to claim 1 and 2, wherein, each described crystalline forming device also comprises temperature regulating device, be used to control the temperature of this crystalline forming device, described temperature regulating device comprises temperature control parts and heater block, described heater block is arranged in the crystalline forming device, and described temperature control parts are electrically connected with crystalline forming device and heater block.
12. equipment according to claim 1, wherein, this equipment also comprises cooling pool, and described cutting part is arranged in cooling pool.
13. continuous producing method of polysilicon, it is characterized in that, this method comprises the solid state si heating and melting, make silicon after the fusion successively by a plurality of crystalline formings district then, the temperature in described a plurality of crystalline formings district descends successively, a crystalline forming district of a plurality of crystalline formings district medial end portions is used to receive the silicon of molten state, and the silicon of molten state is cooled off and crystallization, being arranged in crystalline forming district after the crystalline forming district of described end, to be used to make crystal from the crystalline forming district of described end to continue crystalline forming be banded polysilicon, and this method also comprises cuts described banded polysilicon.
14. method according to claim 13, wherein, described crystalline forming district is 3-15.
15. method according to claim 13, wherein, the polysilicon cooling forming that is arranged so that in each described crystalline forming district is that thickness is the banded polysilicon of 200-300 micron, and the direction of banded polysilicon elongation is perpendicular to the ground.
16. method according to claim 13, wherein, the temperature in the crystalline forming district of described end is 1430-1500 ℃, and the temperature in all the other each crystalline forming districts is all hanged down 100-500 ℃ than the temperature in adjacent previous crystalline forming district.
17. method according to claim 13, wherein, the silicon after the fusion is the 1-3 cm per minute by the speed in each crystalline forming district.
18. method according to claim 13, wherein, the shortest distance in adjacent two crystalline forming districts is 5-15 centimetre.
19. method according to claim 13, wherein, this method comprises that also the silicon to the molten state that begins a crystalline forming district by described end carries out chilling, the silicon of this molten state is cooled to below 1430 ℃ and cooling and crystallization.
20. method according to claim 19, wherein, the method of chilling is 30-100 ℃ a chilling crucible for the lower edge in the crystalline forming district of described end is provided with a temperature, the silicon that makes molten state touches this chilling crucible and crystallisation by cooling treats that crystal structure removes crucible when being molded into more than 8 centimetres.
21. method according to claim 13, wherein, described cutting is carried out in cooling fluid, and the temperature of described cooling fluid is 20-60 ℃, and described cooling fluid is a water.
22. method according to claim 13, wherein, described solid state si is a solar level purity silicon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100892446A CN101565852B (en) | 2008-04-25 | 2008-04-25 | Crystal continuous producing device and method for continuously producing polysilicon by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100892446A CN101565852B (en) | 2008-04-25 | 2008-04-25 | Crystal continuous producing device and method for continuously producing polysilicon by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101565852A CN101565852A (en) | 2009-10-28 |
| CN101565852B true CN101565852B (en) | 2011-10-12 |
Family
ID=41282208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100892446A Expired - Fee Related CN101565852B (en) | 2008-04-25 | 2008-04-25 | Crystal continuous producing device and method for continuously producing polysilicon by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101565852B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051670B (en) * | 2010-11-29 | 2012-06-13 | 奥特斯维能源（太仓）有限公司 | Continuous discharging device without valve control |
| CN104150484A (en) * | 2013-05-13 | 2014-11-19 | 苏州晶科新能源装备科技有限公司 | Enclosed type high purity metal silicon reduction furnace |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1372530A (en) * | 2000-05-11 | 2002-10-02 | 德山株式会社 | Polycrystalline silicon, process and apparatus for producing the same |
| CN1469495A (en) * | 2002-07-19 | 2004-01-21 | 中国科学院广州能源研究所 | Method and special equipment for preparing granular silicon belt |
| CN2708213Y (en) * | 2004-07-08 | 2005-07-06 | 成都蜀菱贸易发展有限公司 | Polysilicon hydrogen reducing furnace |
| CN101109602A (en) * | 2007-08-23 | 2008-01-23 | 浙江精工科技股份有限公司 | Thermal field structure of polysilicon ingot furnace |
-
2008
- 2008-04-25 CN CN2008100892446A patent/CN101565852B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1372530A (en) * | 2000-05-11 | 2002-10-02 | 德山株式会社 | Polycrystalline silicon, process and apparatus for producing the same |
| CN1469495A (en) * | 2002-07-19 | 2004-01-21 | 中国科学院广州能源研究所 | Method and special equipment for preparing granular silicon belt |
| CN2708213Y (en) * | 2004-07-08 | 2005-07-06 | 成都蜀菱贸易发展有限公司 | Polysilicon hydrogen reducing furnace |
| CN101109602A (en) * | 2007-08-23 | 2008-01-23 | 浙江精工科技股份有限公司 | Thermal field structure of polysilicon ingot furnace |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101565852A (en) | 2009-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2089319B1 (en) | Method of purifying metallurgical silicon by directional solidification | |
| JPH11310496A (en) | Production of silicon ingot having unidirectionally solidified texture and apparatus therefor | |
| CN101864594A (en) | Ingot casting method for quasi-monocrystalline silicon | |
| WO2006006436A1 (en) | Method for purifying metal | |
| CN101591808A (en) | Mix directionally solidified casting monocrystalline silicon of germanium and preparation method thereof | |
| CN102197169A (en) | Apparatus and method of use for casting system with independent melting and solidification | |
| CN102312279A (en) | Method for casting crystal by seed crystal induction | |
| CN202989351U (en) | Ingot furnace thermal field structure based on multiple heaters | |
| WO2004036657A1 (en) | Polycrystalline silicon substrate | |
| CN107523858A (en) | A kind of seed crystal laying method, the casting method of class monocrystal silicon and class monocrystalline silicon piece | |
| CN101851782A (en) | Double-cavity heat-insulation cage of second single crystal silicon ingot production furnace | |
| WO2013043627A1 (en) | Method of producing a solar cell | |
| CN101591807A (en) | Directionally solidified casting monocrystalline silicon of nitrating and preparation method thereof | |
| CN101565852B (en) | Crystal continuous producing device and method for continuously producing polysilicon by using same | |
| CN101597787A (en) | Under nitrogen, cast the method for the controlled doped monocrystalline silicon of nitrogen concentration | |
| CN105002557A (en) | Gallium, germanium and boron co-doped polycrystalline silicon and preparation method thereof | |
| CN101981656A (en) | Zone melt recrystallization for inorganic films | |
| CN101477949A (en) | Silicon chip, manufacturing method and apparatus thereof | |
| CN104178809B (en) | A kind of metallurgy method prepares the method for low metal boron foundry alloy | |
| CN101597788B (en) | Method for preparing cast nitrogen-doped monocrystalline silicon through melting polycrystalline silicon under nitrogen | |
| CN106676628A (en) | Preparation method of (100) crystal-orientation small-grain cast multicrystalline silicon | |
| JP2001122696A (en) | Method of producing ribbon silicon wafer | |
| JPS61275119A (en) | Production of silicon ribbon | |
| US6951585B2 (en) | Liquid-phase growth method and liquid-phase growth apparatus | |
| CN202099407U (en) | Crystal growth furnace structure for sapphire crystal growth |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111012 Termination date: 20190425 |