CN103422166A - Quartz crucible for ingotting polycrystalline silicon solar cell, and spraying method thereof - Google Patents
Quartz crucible for ingotting polycrystalline silicon solar cell, and spraying method thereof Download PDFInfo
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- CN103422166A CN103422166A CN2013103352243A CN201310335224A CN103422166A CN 103422166 A CN103422166 A CN 103422166A CN 2013103352243 A CN2013103352243 A CN 2013103352243A CN 201310335224 A CN201310335224 A CN 201310335224A CN 103422166 A CN103422166 A CN 103422166A
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Abstract
The invention discloses a quartz crucible for ingotting a polycrystalline silicon solar cell, and a spraying method of the quartz crucible. The spraying method comprises the following steps: a, preparing a mixing agent, namely dissolving a mixture of silicon powder and silicon nitride powder in a solvent, and uniformly mixing; b, spraying, brushing or infiltrating the mixing agent at the bottom of the quartz crucible to form a mixing agent coating layer; c, drying at the temperature of 20-100 DEG C till the mixing agent coating layer is dried. The crucible for ingotting, manufactured by the method provided by the invention has the advantages that silicon wafer crystal defects are relatively few, the minority carrier lifetime is longer, and the cell efficiency is higher; meanwhile, the crucible is simple to operate, stable in performance and easy to largely and quickly popularize, and additional equipment does not need to be added.
Description
Technical field
The present invention relates to method for manufacturing solar battery, especially a kind of quartz crucible for polysilicon solar battery casting ingot
Spraying method.
Background technology
Crystal-silicon solar cell has high-level efficiency and high stability, is a kind of device of solar generating had superiority most, and wherein polycrystal silicon cell, with higher cost performance, becomes on Vehicles Collected from Market the share occupied more than 80%.But solar battery technology is also immature, photoelectric transformation efficiency is lower, the more high defect of cost of electricity-generating has restricted the solar cell large-scale promotion application.Therefore, improving the cell photoelectric efficiency of conversion and reduce the battery manufacture cost is current photovoltaic industry problem demanding prompt solution.
Polycrystalline silicon solar cell is to make in the polysilicon chip substrate, and lattice defect can the serious efficiency of conversion that reduces solar cell.For the silicon ingot that cuts polysilicon chip, mainly adopt the method for directional freeze to make, the method crystal growing process is controlled coarse, and the silicon ingot volume is large, causes the silicon ingot built-in thermal stress larger.When thermal stresses is greater than the shearing resistance of crystal, stress just discharges in the mode that forms lattice defect.Casting refinement silicon ingot crystal grain, increase crystal boundary density, and the thermal stresses of silicon ingot is discharged by crystal boundary, can reduce the generation of lattice defect, thereby improve battery conversion efficiency.
For the problems referred to above, the technician has carried out some fundamental researchs.For example, Chinese patent CN 102826737 A provide the quartz crucible of a kind of bottom roughened, utilize coarse crucible bottom surface to promote crystal forming core, crystal grain thinning.But, after the crucible spraying silicon nitride coating of roughened, what directly contact with silicon liquid is silicon nitride coating, because silicon nitride coating and silicon liquid do not have wetting property, can not play the effect of nucleating center, thereby it is undesirable that the method is improved effect to grain morphology.The broken silicon material of a kind of use that patent CN 102776557 A propose is layered on crucible bottom and promotes forming core as seed crystal, and the silicon material melts the later stage, and adjusting process keeps broken silicon material partial melting, and crystal be take and do not melted the silicon material as upwards growth of seed crystal, obtains high-quality silicon ingot.But the method is because the silicon material do not melted is arranged at bottom, the silicon ingot percentage of admixture is higher, the yield rate of ingot casting is low, the method needs accurately to control the seed crystal residual content in addition, also can't realize automatic control at present, can only lean on manually and survey with quartz pushrod, the seed crystal residual content is controlled unstable, is difficult to realize popularizing in an all-round way.In addition, prior art also has direct coating silica flour and silicon sol mixture, but silica flour can not be dissolved in silicon sol, and mixture directly is melted, and can't form uniform nucleating center.
Summary of the invention
Goal of the invention: the present invention will provide the spraying method of a kind of quartz crucible for polysilicon solar battery casting ingot and this quartz crucible, so that the crucible obtained can be optimized crystalline-granular texture when manufacturing polysilicon, reduce the defect concentrations in crystals in polysilicon, thereby improve the efficiency of conversion of solar cell.
Technical scheme: a kind of spraying method of quartz crucible for polysilicon solar battery casting ingot comprises the steps:
A, prepare mixture, the mixture of silica flour and silicon nitride powder is dissolved in solvent, stir;
B, by the spraying of described mixture, brush or infiltrate at least part of zone of quartz crucible, form the mixture coating;
C, dry under 20 ~ 100 ℃, until described mixture coating drying.
The purity of described silica flour and silicon nitride powder is equal > 99.9%, particle diameter is 1~200um.In described mixture, the weight ratio of silica flour and silicon nitride powder is 1:10~5:1.After described mixture coating drying, thickness is 1~1000um.
A kind of quartz crucible for polysilicon solar battery casting ingot, the spraying of at least part of zone, brushing or infiltration in described quartz crucible have mixture, the mixture that described mixture is silica flour and silicon nitride.The purity of described silica flour and silicon nitride powder is equal > 99.9%, particle diameter is 1~200um.In described mixture, the weight ratio of silica flour and silicon nitride powder is 1:10~5:1.The coat-thickness that described mixture forms is 1~1000um.
Use above-mentioned crucible ingot casting, the silicon powder particle that silicon liquid be take in above-mentioned mixed deposit layer is nucleating center, at the long brilliant initial stage, forms great number of grains.Crystal grain is when upwards growing, and transverse growth is restricted, and finally obtains crystal particle volume less, and size is even, the silicon ingot that border is mellow and full.Because the crystal boundary distribution is also closeer more even, the thermal stresses of silicon ingot inside is discharged by crystal boundary, thereby has reduced the generation of the lattice defects such as dislocation.Owing to having there is more uniform type epipole, so crystal grain is more even.Silicon nitride one in mixture is make that coating is combined with crucible bottom tightr, the 2nd, and its fusing point is higher, and the silica flour in can supercoat is not melted, thereby as nucleating center.
Beneficial effect: the crucible ingot casting that uses the inventive method to make, still less, minority carrier life time is higher for the silicon chip lattice defect, and the polysilicon chip battery efficiency has improved 0.3~0.5% than conventional batteries; The ingot casting cost is suitable with conventional ingot casting simultaneously; Simple to operate, product performance are stable, do not need to increase extras, are easy to a large amount of Rapid Popularizations.
The accompanying drawing explanation
Fig. 1 is experiment effect figure of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing to the present invention's detailed explanation in addition:
By silica flour and the silicon nitride powder that purity is greater than 99.9%, particle diameter is less than 100um, according to weight ratio 1:8, mix, be dissolved in the solvent that 300mL prepares, be mixed with mixture; The crucible inwall is according to the common process spraying silicon nitride coating, after the coating drying, at half spraying mixture of crucible bottom.Keep crucible temperature be 25 ℃ to the mixture complete drying, the about 0.1mm of deposit thickness; According to conventional casting ingot process charging, ingot casting.Got, without spraying mixture part little side's ingot, contrast grain morphology, corrosion default, test minority carrier life time are also collected whole silicon chips and are carried out the battery efficiency contrast, comparing result as shown in Figure 1.
Comparing result is as follows:
Nucleating agent is arranged | Without nucleating agent | |
Crystal grain diameter/ |
3~6 | 8~20 |
Average minority carrier lifetime/us | 5.9 | 6.3 |
The average cell efficiency of conversion | 17.82% | 17.45% |
Embodiment 2
By silica flour and the silicon nitride powder that purity is greater than 99.9%, particle diameter is less than 100um, according to weight ratio 1:10, mix, be dissolved in the solvent that 300mL prepares, be mixed with mixture; The crucible inwall is according to the common process spraying silicon nitride coating, after the coating drying, at half spraying mixture of crucible bottom.Keep crucible temperature be 35 ℃ to the mixture complete drying, the about 0.3mm of deposit thickness; According to conventional casting ingot process charging, ingot casting.Got, without spraying mixture part little side's ingot, contrast grain morphology, corrosion default, test minority carrier life time are also collected whole silicon chips and are carried out the battery efficiency contrast.
Comparing result is as follows:
Nucleating agent is arranged | Without nucleating agent | |
Crystal grain diameter/mm | 2~6 | 7~18 |
Average minority carrier lifetime/us | 6.0 | 6.2 |
The average cell efficiency of conversion | 17.79% | 17.41% |
By silica flour and the silicon nitride powder that purity is greater than 99.9%, particle diameter is less than 100um, according to weight ratio 1:6, mix, be dissolved in the solvent that 300mL prepares, be mixed with mixture; The crucible inwall is according to the common process spraying silicon nitride coating, after the coating drying, at half spraying mixture of crucible bottom.Keep crucible temperature be 50 ℃ to the mixture complete drying, the about 0.2mm of deposit thickness; According to conventional casting ingot process charging, ingot casting.Got, without spraying mixture part little side's ingot, contrast grain morphology, corrosion default, test minority carrier life time are also collected whole silicon chips and are carried out the battery efficiency contrast.
Comparing result is as follows:
Nucleating agent is arranged | Without nucleating agent | |
Crystal grain diameter/mm | 2~6 | 10~20 |
Average minority carrier lifetime/us | 6.5 | 6.0 |
The average cell efficiency of conversion | 17.85% | 17.47% |
Embodiment 4
By silica flour and the silicon nitride powder that purity is greater than 99.9%, particle diameter is less than 100um, according to weight ratio 1:2, mix, be dissolved in the solvent that 300mL prepares, be mixed with mixture; The crucible inwall is according to the common process spraying silicon nitride coating, after the coating drying, at half spraying mixture of crucible bottom.Keep crucible temperature be 60 ℃ to the mixture complete drying, the about 0.5mm of deposit thickness; According to conventional casting ingot process charging, ingot casting.Got, without spraying mixture part little side's ingot, contrast grain morphology, corrosion default, test minority carrier life time are also collected whole silicon chips and are carried out the battery efficiency contrast.
Comparing result is as follows:
Nucleating agent is arranged | Without nucleating agent | |
Crystal grain diameter/mm | 2~5 | 8~20 |
Average minority carrier lifetime/us | 6.6 | 6.4 |
The average cell efficiency of conversion | 17.82% | 17.41% |
Embodiment 5
By silica flour and the silicon nitride powder that purity is greater than 99.9%, particle diameter is less than 100um, according to weight ratio 1:2, mix, be dissolved in the solvent that 300mL prepares, be mixed with mixture; The crucible inwall is according to the common process spraying silicon nitride coating, after the coating drying, at half spraying mixture of crucible bottom.Keep crucible temperature be 70 ℃ to the mixture complete drying, the about 0.7mm of deposit thickness; According to conventional casting ingot process charging, ingot casting.Got, without spraying mixture part little side's ingot, contrast grain morphology, corrosion default, test minority carrier life time are also collected whole silicon chips and are carried out the battery efficiency contrast.
Comparing result is as follows:
Nucleating agent is arranged | Without nucleating agent | |
Crystal grain diameter/mm | 2~5 | 7~20 |
Average minority carrier lifetime/us | 6.4 | 6.1 |
The average cell efficiency of conversion | 17.79% | 17.42% |
Embodiment 6
By silica flour and the silicon nitride powder that purity is greater than 99.9%, particle diameter is less than 100um, according to weight ratio 1:1, mix, be dissolved in the solvent that 300mL prepares, be mixed with mixture; The crucible inwall is according to the common process spraying silicon nitride coating, after the coating drying, at half spraying mixture of crucible bottom.Keep crucible temperature be 80 ℃ to the mixture complete drying, the about 0.9mm of deposit thickness; According to conventional casting ingot process charging, ingot casting.Got, without spraying mixture part little side's ingot, contrast grain morphology, corrosion default, test minority carrier life time are also collected whole silicon chips and are carried out the battery efficiency contrast.
Comparing result is as follows:
Nucleating agent is arranged | Without nucleating agent | |
Crystal grain diameter/mm | 2~5 | 9~20 |
Average minority carrier lifetime/us | 6.6 | 6.1 |
The average cell efficiency of conversion | 17.85% | 17.46% |
Embodiment 7
By silica flour and the silicon nitride powder that purity is greater than 99.9%, particle diameter is less than 100um, according to weight ratio 2:1, mix, be dissolved in the solvent that 300mL prepares, be mixed with mixture; The crucible inwall is according to the common process spraying silicon nitride coating, after the coating drying, at half spraying mixture of crucible bottom.Keep crucible temperature be 90 ℃ to the mixture complete drying, the about 1mm of deposit thickness; According to conventional casting ingot process charging, ingot casting.Got, without spraying mixture part little side's ingot, contrast grain morphology, corrosion default, test minority carrier life time are also collected whole silicon chips and are carried out the battery efficiency contrast.
Comparing result is as follows:
Nucleating agent is arranged | Without nucleating agent | |
Crystal grain diameter/mm | 2~5 | 7~18 |
Average minority carrier lifetime/us | 6.4 | 5.9 |
The average cell efficiency of conversion | 17.80% | 17.46% |
Embodiment 8
By silica flour and the silicon nitride powder that purity is greater than 99.9%, particle diameter is less than 100um, according to weight ratio 5:1, mix, be dissolved in the solvent that 300mL prepares, be mixed with mixture; The crucible inwall is according to the common process spraying silicon nitride coating, after the coating drying, at half spraying mixture of crucible bottom.Keep crucible temperature be 100 ℃ to the mixture complete drying, the about 1um of deposit thickness; According to conventional casting ingot process charging, ingot casting.Got, without spraying mixture part little side's ingot, contrast grain morphology, corrosion default, test minority carrier life time are also collected whole silicon chips and are carried out the battery efficiency contrast.
Comparing result is as follows:
Nucleating agent is arranged | Without nucleating agent | |
Crystal grain diameter/mm | 2~5 | 8~18 |
Average minority carrier lifetime/us | 6.3 | 5.9 |
The average cell efficiency of conversion | 17.81% | 17.49% |
Claims (8)
1. the spraying method of a quartz crucible for polysilicon solar battery casting ingot, is characterized in that, comprises the steps:
A, prepare mixture, the mixture of silica flour and silicon nitride powder is dissolved in solvent, stir;
B, by the spraying of described mixture, brush or infiltrate at least part of zone of quartz crucible, form the mixture coating;
C, dry under 20 ~ 100 ℃, until described mixture coating drying.
2. the spraying method of quartz crucible for polysilicon solar battery casting ingot as claimed in claim 1, is characterized in that, the purity of described silica flour and silicon nitride powder is equal > 99.9%, particle diameter is 1~200um.
3. the spraying method of quartz crucible for polysilicon solar battery casting ingot as claimed in claim 1 or 2, is characterized in that, in described mixture, the weight ratio of silica flour and silicon nitride powder is 1:10~5:1.
4. the spraying method of quartz crucible for polysilicon solar battery casting ingot as claimed in claim 1 or 2, is characterized in that, after described mixture coating drying, thickness is 1~1000um.
5. a quartz crucible for polysilicon solar battery casting ingot, is characterized in that, the spraying of at least part of zone, brushing or infiltration in described quartz crucible have mixture, the mixture that described mixture is silica flour and silicon nitride powder.
6. the spraying method of quartz crucible for polysilicon solar battery casting ingot as claimed in claim 5, is characterized in that, the purity of described silica flour and silicon nitride powder is equal > 99.9%, particle diameter is 1~200um.
7. as the spraying method of claim 5 or 6 described quartz crucible for polysilicon solar battery casting ingot, it is characterized in that, in described mixture, the weight ratio of silica flour and silicon nitride powder is 1:10~5:1.
8. as the spraying method of claim 5 or 6 described quartz crucible for polysilicon solar battery casting ingot, it is characterized in that, the coat-thickness that described mixture forms is 1~1000um.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104195632A (en) * | 2014-09-04 | 2014-12-10 | 奥特斯维能源(太仓)有限公司 | Method for casting high efficiency polycrystalline silicon ingots |
CN104711673A (en) * | 2015-03-13 | 2015-06-17 | 湖南红太阳光电科技有限公司 | Preparation method of polycrystalline silicon ingot |
CN105369351A (en) * | 2015-12-17 | 2016-03-02 | 江西赛维Ldk太阳能高科技有限公司 | Polycrystalline silicon ingot, preparation method thereof and polycrystalline silicon chip |
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JPH11236291A (en) * | 1998-02-25 | 1999-08-31 | Mitsubishi Materials Corp | Crucible for producing silicon ingot having unidirectionally solidified polycrystalline structure |
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CN101913776A (en) * | 2010-09-03 | 2010-12-15 | 山东理工大学 | Preparation method of silicon nitride coating quartz crucible |
CN102515851A (en) * | 2011-12-26 | 2012-06-27 | 天津大学 | Preparation method for silicon-nitride-based coating on surface of porous ceramic |
CN102776561A (en) * | 2012-04-01 | 2012-11-14 | 江西赛维Ldk太阳能高科技有限公司 | Polycrystalline silicon ingot, preparation method of polycrystalline silicon ingot, polycrystalline silicon slice and crucible for polycrystalline silicon ingot casting |
CN102884024A (en) * | 2010-02-15 | 2013-01-16 | H.C.施塔克股份有限公司 | Crucible for photovoltaics |
CN202898597U (en) * | 2012-10-26 | 2013-04-24 | 阿特斯(中国)投资有限公司 | Crucible for silicon ingot |
JP2013112581A (en) * | 2011-11-30 | 2013-06-10 | Sharp Corp | Crucible, production method of polycrystalline silicon ingot, polycrystalline silicon ingot, polycrystalline silicon wafer, polycrystalline silicon solar cell, and polycrystalline solar cell module |
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2013
- 2013-08-05 CN CN2013103352243A patent/CN103422166A/en active Pending
Patent Citations (8)
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JPH11236291A (en) * | 1998-02-25 | 1999-08-31 | Mitsubishi Materials Corp | Crucible for producing silicon ingot having unidirectionally solidified polycrystalline structure |
CN101255002A (en) * | 2006-12-21 | 2008-09-03 | 肖特股份有限公司 | Quartz glass body, method and casting mold for manufacturing the same |
CN102884024A (en) * | 2010-02-15 | 2013-01-16 | H.C.施塔克股份有限公司 | Crucible for photovoltaics |
CN101913776A (en) * | 2010-09-03 | 2010-12-15 | 山东理工大学 | Preparation method of silicon nitride coating quartz crucible |
JP2013112581A (en) * | 2011-11-30 | 2013-06-10 | Sharp Corp | Crucible, production method of polycrystalline silicon ingot, polycrystalline silicon ingot, polycrystalline silicon wafer, polycrystalline silicon solar cell, and polycrystalline solar cell module |
CN102515851A (en) * | 2011-12-26 | 2012-06-27 | 天津大学 | Preparation method for silicon-nitride-based coating on surface of porous ceramic |
CN102776561A (en) * | 2012-04-01 | 2012-11-14 | 江西赛维Ldk太阳能高科技有限公司 | Polycrystalline silicon ingot, preparation method of polycrystalline silicon ingot, polycrystalline silicon slice and crucible for polycrystalline silicon ingot casting |
CN202898597U (en) * | 2012-10-26 | 2013-04-24 | 阿特斯(中国)投资有限公司 | Crucible for silicon ingot |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104195632A (en) * | 2014-09-04 | 2014-12-10 | 奥特斯维能源(太仓)有限公司 | Method for casting high efficiency polycrystalline silicon ingots |
CN104711673A (en) * | 2015-03-13 | 2015-06-17 | 湖南红太阳光电科技有限公司 | Preparation method of polycrystalline silicon ingot |
CN105369351A (en) * | 2015-12-17 | 2016-03-02 | 江西赛维Ldk太阳能高科技有限公司 | Polycrystalline silicon ingot, preparation method thereof and polycrystalline silicon chip |
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