Background technology
Solar energy power generating is one of form of sustainable energy utilization with fastest developing speed at present, was obtained in the last few years develops rapidly in various countries.In photovoltaic industry, raising electricity conversion and reduction production cost are two important targets always.At present, application solar cell material the most general is crystalline silicon material, comprises silicon single crystal and polycrystalline silicon material, and the most outstanding feature of crystal silicon solar energy battery is its stability and high efficiency.
Current sun power silicon single crystal is mainly obtained by vertical pulling method (CZ method), has the high efficiency feature of low defect, and can be formed the texture of pyramid by the method for alkali making herbs into wool, improves the absorption to light, thus improves transformation efficiency.But also there is the higher shortcoming of production cost in silicon single crystal simultaneously.Polysilicon obtains mainly through the method for directional freeze (casting), and it has captured photovoltaic market over half with the advantage that production cost is lower.But there is a large amount of dislocations and crystal boundary in polysilicon, they and impurity effect can be introduced deep energy level and reduce the diffusion length of minority carrier thus the efficiency of conversion of reduction polysilicon solar cell in silicon.In addition, owing to there is multiple grain orientation in polysilicon, anisotropic high-efficient alkali etching method is not suitable for polysilicon chip, and above factor makes the efficiency of conversion of polycrystal silicon cell 1-2 percentage point lower than monocrystalline silicon battery.Simultaneously owing to containing a large amount of crystal boundaries and dislocation in polysilicon, comparatively silicon single crystal is low to cause physical strength, makes polysilicon chip easily fragmentation in production, processing, battery preparation and assembling components process, increases production cost.At present, silicon single crystal can cell piece efficiency of conversion is high, physical strength is high advantage and the low advantages of Foundry Production production cost get up very much by casting monocrystalline silicon, becomes the emphasis of research.Chinese patent application 200910152970.2 discloses a kind of method controlling bottom seed of single crystal silicon and not exclusively melt, its mode mainly opening heat-insulation cage by the heat fused stage controls crucible bottom temperature, but this method can consume higher due to the heat radiation bottom the fusion stage, and controllability is poor.
Therefore, exploitation is further needed to be used for the modifying device of growing single-crystal silicon by directional solidification method.
Summary of the invention
In view of the problems referred to above of prior art, this invention exploits a kind of device for growing single-crystal silicon by directional solidification method of improvement, this device by installing around whole crucible guard boards the fusing that heat insulation device controls seed crystal at crucible guard boards outer bottom gusset, the problem that bottom when solving growing single-crystal silicon by directional solidification method, seed crystal melts completely.This device is very little to the transformation of equipment, and energy consumption is little, and cost is low, and controllability is strong, easy handling, is applicable to large-scale production.
First object of the present invention is to provide a kind of device for growing single-crystal silicon by directional solidification method, this device at least comprises body of heater (13), for supporting the pillar (15) of body of heater, by the heat exchange mass (4) of shore supports, be placed on the crucible guard boards (8) in heat exchange mass, the quartz crucible (9) for taking up silicon material in crucible guard boards, be fixed on the well heater (7) on quartz rod (14), and the side heat-insulation cage (3) to be controlled by movable rod (6), it is characterized in that, at crucible guard boards outer bottom gusset around whole crucible guard boards, heat insulation device (10) is installed.
According to one of the present invention, preferred embodiment described heat insulation device can be made up of carbon back lagging material, and described carbon back lagging material includes but not limited to graphite and carbon/carbon compound material, also can be made up of porous ceramic film material or asbestos.The shape of heat insulation device can be bulk, tabular or band shape.
According to of the present invention one preferred embodiment, the thickness of described heat insulation device is 2-10cm, is highly 2-20cm; Preferred thickness is 3-5cm, is highly 4-12cm.
According to of the present invention one preferred embodiment, described heat insulation device can use molybdenum filament, tungsten filament, graphite rope, ceramic nut or the nut be made up of molybdenum, tungsten or graphite material to be secured on crucible guard boards.
This heat insulation device can in the process of heating, and make the heat of well heater be difficult to arrive crucible inner bottom part, the convection circulation by means of only crucible inside is heated bottom, thus regulates heterogeneity phantom in crucible, controls bottom seed crystal and not exclusively melts.By quartz rod subsidiary, the actual melting rate of monocrystalline and theoretical assessment closely, illustrate that this process controllability is strong.
Second object of the present invention is to provide the method using said apparatus growing single-crystal silicon by directional solidification method, said method comprising the steps of:
(1) crucible is placed in using as the silicon single crystal material of seed crystal, polycrystalline silicon material and doping agent successively;
(2) fusion stage: heating silicon material, makes seed crystal melt 10%-90%;
(3) in the long brilliant stage: the temperature reducing well heater, the liquation of silicon, the melted silicon of polycrystalline silicon material and the fusing of part seed crystal, along seed crystal crystal orientation directional solidification growth, obtains the silicon single crystal in crystal orientation identical with seed crystal after annealing cooling.
According to of the present invention one preferred embodiment, seed crystal described in step (1) is the monocrystalline silico briquette in <100> crystal orientation.
According to one of the present invention, preferred embodiment described in step (1), seed crystal is long 10-16cm, wide 10-16cm, the prismatic single crystal silico briquette of high 0.5-5cm.
According to of the present invention one preferred embodiment, described in step (1), seed crystal is laid in crucible bottom.More preferably, when laying seed crystal, its mutual close contact is made.
According to of the present invention one preferred embodiment, described in step (1), doping agent is selected from boron, gallium, phosphorus, arsenic or antimony.
According to one of the present invention, preferred embodiment step (2) and (3) are carried out in a vacuum or inert atmosphere, preferably carry out under vacuum or argon gas atmosphere.
According to of the present invention one preferred embodiment, quartz rod can be used in step (2) to carry out the height of the molten single crystal seed of subsidiary crucible bottom.
Preferred embodiment when step (2) fusion stage seed crystal starts to melt, bottom heat exchange mass, rare gas element is passed into, preferred argon gas, for keeping the stable of crucible bottom temperature according to one of the present invention.
According to of the present invention one preferred embodiment, after entering the fusion stage, heater temperature is adjusted to 1500-1560 DEG C, when crucible bottom temperature rises to 1360-1390 DEG C, argon gas is passed into bottom heat exchange mass, treat that polysilicon melts completely, when the seed crystal of crucible bottom melts 10%-90%, enter the long brilliant stage.
According to of the present invention one preferred embodiment, in the long brilliant process of step (3), well heater is progressively cooled to 1400-1430 DEG C, and side heat-insulation cage slowly opens 10-17cm.
According to a particularly preferred embodiment of the present invention, in the long brilliant stage, first heater temperature is down to 1420-1430 DEG C fast, subsequently side heat-insulation cage is opened 3-5cm.Heater temperature is down to 1400-1410 DEG C gradually, and side heat-insulation cage is opened simultaneously, preferably opens 10-17cm, reaches stable long crystalline state.
The invention has the beneficial effects as follows: the device providing a kind of effective growing single-crystal silicon, the crystal orientation of the silicon single crystal obtained by this device is identical, and gained cell piece cost is lower, and efficiency is higher.Whole technique can be carried out in existing polycrystalline silicon ingot or purifying furnace, and cost is low, easy handling and accomplishing scale production.
Embodiment
As shown in Figure 1, the device that the present invention is used for growing single-crystal silicon by directional solidification method comprises body of heater 13, the end thermal baffle 12 supported by pillar 15 and heat exchange mass 4, heat exchange mass 4 is placed crucible guard boards 8 and crucible 9, single crystal seed 1 and polycrystalline silicon material 2 is taken up in crucible 13, crucible guard boards 8 exterior bottom is provided with heat insulation device 10, side heat-insulation cage 3, top thermal baffle 11 and end thermal baffle 12 form heat-insulation cage system, the open and close of side heat-insulation cage 3 is controlled by movable rod 6, in melting process, preferably use the fusing degree of quartz rod 14 subsidiary single crystal seed.
Embodiment 1
Around whole crucible guard boards, thickness 5cm is installed all around in crucible guard boards exterior bottom, the graphite thermal baffle of height 12cm, uses molybdenum filament to fix.Then be 3cm by 36 pieces of thickness, sectional dimension be 126 × 126mm, <100> crystal orientation monocrystalline silico briquette by 6 × 6 mode to tile crucible bottom, close contact between silico briquette.Again virgin polycrystalline silicon material is placed on above seed crystal, and puts into doping agent boron, make the target resistivity after doping be 1.70 Ω cm.Be positioned in ingot furnace by charged crucible and vacuumize, in heating phase stove, vacuum state and argon gas atmosphere alternately, are beneficial to impurities removal.Fusion stage, heater temperature to 1560 DEG C, now polysilicon melts completely, by quartz rod subsidiary, when single crystal seed melts 60%, enters the long brilliant stage.In long brilliant process, first heater temperature is down to 1430 DEG C fast by 1560 DEG C, opens 5cm with rear side heat-insulation cage, and then heater temperature is down to 1410 DEG C step by step, and side heat-insulation cage opens 10cm simultaneously, is now the stable long brilliant stage.The current consumption of this technological process, compared with documents method, can reduce 6%.
Embodiment 2
Install thickness 3cm around whole crucible guard boards all around in crucible guard boards outer lower side, the graphite thermal baffle of height 4cm, fixes with graphite screw.Be 5cm by 25 pieces of thickness, sectional dimension be 156 × 156mm, <100> crystal orientation monocrystalline silico briquette by 5 × 5 mode to tile crucible bottom, close contact between silico briquette.Virgin polycrystalline silicon material is placed on above seed crystal, puts into doping agent boron, make the target resistivity after doping be 1.70 Ω cm.Charged crucible is positioned in ingot furnace and vacuumizes; In heating phase stove, vacuum state and argon gas atmosphere alternately, are beneficial to impurities removal.After entering the fusion stage, heater temperature to 1500 DEG C, now polysilicon melts completely, when quartz rod subsidiary determination single crystal seed melts 40%, enters the long brilliant stage.In long brilliant process, first heater temperature is down to 1420 DEG C fast, opens 3cm with rear side heat-insulation cage, and then heater temperature is down to 1400 DEG C, and side heat-insulation cage opens 17cm, reaches stable long crystalline state.The current consumption of this technological process, compared with documents method, can reduce 5%.
The specific embodiment more than enumerated, only for the present invention is described further, does not represent protection scope of the present invention and is only limitted to this.