CN101800266B - Preparation method of selective emitting electrode crystal silicon solar battery - Google Patents
Preparation method of selective emitting electrode crystal silicon solar battery Download PDFInfo
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- CN101800266B CN101800266B CN2010101236193A CN201010123619A CN101800266B CN 101800266 B CN101800266 B CN 101800266B CN 2010101236193 A CN2010101236193 A CN 2010101236193A CN 201010123619 A CN201010123619 A CN 201010123619A CN 101800266 B CN101800266 B CN 101800266B
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Abstract
The invention discloses a preparation method of a selective emitting electrode crystal silicon solar battery. The method of the invention is characterized in that a method for naturally forming a phosphor-silicon glass layer on a P-N node when growing the P-N node on a silicon substrate is utilized, and the phosphor-silicon glass layer under an electrode region is maintained by adopting a screen printing method. Because the phosphor-silicon glass layer has higher phosphor atom content, re-diffusion is carried out on the phosphor-silicon glass layer under the electrode region so that the phosphor atoms in the phosphor-silicon glass layer are diffused into a silicon sheet body. Thereby, a transverse n<+>/n node and a vertical n<+>/p node are formed at a grid line electrode for forming a selective emitting electrode crystal silicon solar battery. The method has the advantages that the method is compatible to the crystal silicon solar battery industrialized production process, additional equipment does not need to be added, the cost is low, the repeatability is good, and the invention is suitable for industrial mass production.
Description
Technical field
The present invention relates to the preparation method of solar cell, specifically be meant a kind of preparation method of selective emitter crystalline silicon solar cell.
Background technology
Solar power generation is one of very fast clean energy resource of development in recent years.In at present all solar power generations, crystalline silicon (comprising monocrystalline silicon and polysilicon) solar battery product has occupied about 90% the market share.Provide a kind of prospect of low-cost product although comprise the hull cell of amorphous silicon battery,, can't replace crystal silicon cell fully at present owing to the not high reason of conversion efficiency.Therefore, we can say, reduce the solar cell cost, mainly still reduce the cost of crystal silicon solar energy battery.Reducing the cost of crystal silicon solar energy battery mainly can set about from two aspects: use thin more crystalline silicon substrate material 1..2. obtain higher cell conversion efficiency.Be to obtain higher cell conversion efficiency, people have proposed the selective emitting electrode structure crystal silicon solar energy battery, compare with conventional crystal silicon solar energy battery structure, and the selective emitter battery is many horizontal n under the front surface grid line
+/ n knot and one is n longitudinally
+/ p knot, this structure helps improving the collection of photo-generated carrier, the particularly collection of shortwave photo-generated carrier, thus improve short circuit current Isc.At high-doped zone, the easy and electrode formation ohmic contact of crystalline silicon, the series resistance of reduction solar cell improves fill factor, curve factor FF.In doped regions, lower impurity concentration can reduce the recombination probability of minority carrier, reduces the reverse saturation current of battery, improves open circuit voltage and short circuit current, finally can obtain higher cell conversion efficiency.
The preparation method who realizes the selective emitter crystalline silicon solar cell structure at present mainly contains two step diffusion method and single portion diffusion methods.Two step diffusion methods refer to the phosphorus source of High temperature diffusion variable concentrations at twice, obtain high low doped region.The single step diffusion generally is meant the impurity diffusion source of throwing in different amounts in the zones of different of silicon chip surface, puts into diffusion furnace subsequently and carries out High temperature diffusion.The method that adopt usually in the laboratory is: at first use laser in the silicon chip surface cutting, coat the phosphorus slurry at silicon chip surface again, the phosphorus slurry amount that obtains in cutting is bigger than the cutting outside, adopts the single step diffusion method to form high doped regions then.Perhaps adopt two step diffusion methods, promptly silicon chip surface is coated the back formation of phosphorus slurry and carry out High temperature diffusion, in cutting, add the phosphorus slurry more once more, carry out High temperature diffusion, form high doped regions.The shortcoming of this method is the cost height, and laser costs an arm and a leg, and complex process, and production efficiency is not high.Also the someone adopts when printing electrode and mix the high concentration phosphorus slurry in electrode slurry, and is highly doped in the acquisition of electrode contact zone behind the sintering like this, but because the electrode sintering time is shorter, and phosphorus atoms can not be diffused into the silicon chip depths, therefore, effect is undesirable.
Summary of the invention
The purpose of this invention is to provide a kind of with the conventional industrialized producing technology preparation method of compatible selective emitter crystalline silicon solar cell mutually, this method does not need to add extra equipment, and is with low cost, and good reproducibility is fit to industrial mass manufacture.
Technical scheme of the present invention is: utilize when growth P-N ties on silicon chip, tie the phosphorosilicate glass layer that nature forms at P-N, adopt the method for silk screen printing, keep the phosphorosilicate glass layer under the electrode district, because phosphorosilicate glass layer contains higher phosphorus atoms, this phosphorosilicate glass layer is spread again, the phosphorus atoms in the phosphorosilicate glass layer is diffused in the wafer bulk, thereby form a horizontal n at the grid place
+/ n knot and one is n longitudinally
+/ p knot constitutes a selective emitter crystalline silicon solar cell.
Concrete preparation process of the present invention is as follows:
A. after at first the crystalline silicon substrate being carried out conventional cleaning and process for etching, put into diffusion furnace and carry out conventional phosphorus atoms diffusion, on the crystalline silicon substrate, form P-N knot layer, make N type laminar surface phosphorus atoms concentration reach 10
21Cm
-3, naturally form phosphorosilicate glass layer that one deck contain phosphorus atoms at the N of silicon chip type laminar surface this moment.
B. adopt silk screen print method to print one deck photoresist pattern then on the phosphorosilicate glass layer of silicon chip, used photoresist half tone figure is similar to the half tone graphics shape of printed silver gate line electrode.Difference is, the main grid width of photoresist half tone is greater than silver grating line electrode network edition owner grid width 1-2mm, the thin grid line width of photoresist half tone is greater than the thin grid line width of silver grating line electrode half tone 0.18-0.22mm, and the thin grating spacing of photoresist half tone is less than the thin grating spacing 0.2-0.25mm of silver grating line electrode half tone.Its objective is: though screen process press repeatedly pressroom have machine error, can guarantee that also metal silver grating line electrode is printed on the heavily doped region of phosphorus, form good Ohmic contact.The crystalline silicon substrate that will print the photoresist pattern is again put into heat-treatment furnace, carries out Low Temperature Heat Treatment under 200-300 ℃, and photoresist is solidified.
C. use hydrofluoric acid to remove the phosphorosilicate glass layer that the silicon chip surface does not have the photoresist protection.
D. utilize sulfuric acid solution to remove photoresist, make the N type laminar surface of silicon chip expose the phosphorosilicate glass figure that generates by the photoresist half tone.
E. above-mentioned silicon chip is carried out The high temperature anneal, annealing temperature is 800-1000 ℃, makes that phosphorus atoms diffuses in the wafer bulk in the phosphorosilicate glass layer on silicon chip surface, thereby forms a horizontal n at the grid place
+/ n knot and one is n longitudinally
+/ p knot.
The aluminium back of the body field of F. using conventional plasma chemical vapor deposition (PECVD) grown silicon nitride film and silk screen print method to prepare the argent gate line electrode and the back side is carried out high temperature sintering at last, forms selective emitter crystalline silicon solar cell.
Said crystalline silicon comprises monocrystalline silicon and polysilicon.
Preparation method's of the present invention advantage is: utilize the phosphorosilicate glass layer that forms naturally in P-N knot growth course, spread, obtain high doped regions, thereby form a horizontal n at the gate line electrode place
+/ n knot and one is n longitudinally
+/ p knot constitutes a selective emitter crystalline silicon solar cell, and this method is compatible mutually with the crystal silicon solar energy battery industrialized producing technology, does not need to add extra equipment, and is with low cost, and good reproducibility is fit to industrial mass manufacture.
Description of drawings
Fig. 1 is the structural representation of crystal silicon solar cell with selective emitter of the present invention.
Fig. 2 generates the structural representation of phosphorosilicate glass layer for the phosphorous diffusion rear surface.
Fig. 3 is the structural representation behind the silk screen printing photoresist.
Fig. 4 is for removing the structural representation behind the phosphorosilicate glass do not have the photoresist protection.
Fig. 5 presses the phosphorosilicate glass figure that the photoresist half tone generates after removing photoresist.
Fig. 6 is the structural representation in the different levels of doping zone after handling through High temperature diffusion.
Fig. 7 is the used silk screen printing photoresist half tone structural representation of present embodiment.
Fig. 8 is the used silk screen printing silver grating line electrode network plate structure schematic diagram of present embodiment.
Embodiment
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail:
Related crystal silicon solar cell with selective emitter structure as shown in Figure 1, wherein 1 is the silver grating line electrode, 2 are the aluminium back of the body, the n among the figure
+, n and p form a horizontal n respectively at the gate line electrode place
+/ n knot and one is n longitudinally
+/ p knot forms a p-n junction at gate line electrode with outskirt.
The concrete steps of present embodiment are as follows:
1.P behind cleaning of type crystalline silicon substrate (comprising monocrystalline silicon and polysilicon) process and the process for etching, put into diffusion furnace and carry out conventional phosphorus atoms diffusion, about about 40 Ω of diffusion back silicon chip surface square resistance/, and grow the phosphorosilicate glass layer 3 that one deck contains phosphorus atoms at silicon chip surface, surperficial phosphorus atoms concentration reaches 10
21Cm
-3About, see Fig. 2.
2. use silk screen print method printing coating on the phosphorosilicate glass layer 3 of silicon chip to carve glue 4 (can be positive glue or negative glue),, photoresist is solidified, see Fig. 3 then 200-300 ℃ of following Low Temperature Heat Treatment.The used photoresist half tone of silk screen print method as shown in Figure 7.Similar to the half tone graphics shape of printed silver gate line electrode, see Fig. 8.Difference is that the main grid width of photoresist half tone is increased to 3mm from 2mm, and thin grid line width is increased to 0.32mm from 0.12mm, and thin grating spacing reduces to 2.5mm from 2.7mm.She Ji purpose is like this, though screen process press repeatedly pressroom have machine error, can guarantee that also metal silver grating line electrode is printed on the heavily doped region of phosphorus, form good Ohmic contact, thereby the stability that improves production technology is with repeatable.
3. silicon chip is put into hydrofluoric acid, remove the phosphorosilicate glass layer that silicon chip surface does not have the photoresist protection, take out subsequently, rinse well, see Fig. 4 with deionized water.
4. silicon chip is put into sulfuric acid solution, under 40 ℃ of temperature, remove photoresist 4, make and expose the phosphorosilicate glass figure that generates by the photoresist half tone on the silicon chip front surface, see Fig. 5.
5. above-mentioned silicon chip is put into diffusion furnace or annealing furnace, high annealing in air, 900 ℃ of annealing temperatures make that phosphorus atoms diffuses in the wafer bulk in the phosphorosilicate glass layer on silicon chip surface, thereby under gate line electrode, form high phosphorus doped in concentrations profiled district, form a horizontal n
+/ n knot and one is n longitudinally
+/ p knot.Again silicon chip is put into hydrofluoric acid and removed remaining phosphorosilicate glass, remove the silicon chip edge part with the method for plasma etching subsequently, see Fig. 6.
6. use conventional pecvd process grown silicon nitride film 5,,, carry out high temperature sintering at last, form selective emitter crystalline silicon solar cell, see Fig. 1 with the aluminium back of the body field 2 at the silk screen print method printed silver gate line electrode 1 and the back side as antireflective film.
Claims (2)
1. the preparation method of a selective emitter crystalline silicon solar cell is characterized in that concrete preparation process is as follows:
A. at first the crystalline silicon substrate is carried out conventional cleaning and process for etching, then put into diffusion furnace and carry out conventional phosphorus atoms diffusion, on the crystalline silicon substrate, form P-N knot layer, make N type laminar surface phosphorus atoms concentration reach 10
21Cm
-3, naturally form phosphorosilicate glass layer that one deck contain phosphorus atoms at the N of silicon chip type laminar surface this moment;
B. adopt silk screen print method to print one deck photoresist pattern then on the phosphorosilicate glass layer of silicon chip, used photoresist half tone figure is similar to the half tone graphics shape of printed silver gate line electrode; Difference is, the main grid width of photoresist half tone is greater than silver grating line electrode network edition owner grid width 1-2mm, the thin grid line width of photoresist half tone is greater than the thin grid line width of silver grating line electrode half tone 0.18-0.22mm, and the thin grating spacing of photoresist half tone is less than the thin grating spacing 0.2-0.25mm of silver grating line electrode half tone; The crystalline silicon substrate that will print the photoresist pattern is again put into heat-treatment furnace, carries out Low Temperature Heat Treatment under 200-300 ℃, and photoresist is solidified;
C. use hydrofluoric acid to remove the phosphorosilicate glass layer that the silicon chip surface does not have the photoresist protection;
D. utilize sulfuric acid solution to remove photoresist, make the N type laminar surface of silicon chip expose the phosphorosilicate glass figure that generates by the photoresist half tone;
E. above-mentioned silicon chip is carried out The high temperature anneal, annealing temperature is 800-1000 ℃, makes that phosphorus atoms diffuses in the silica-based lamellar body in the phosphorosilicate glass layer on silicon chip surface, thereby forms a horizontal n at the gate line electrode place
+/ n knot and one is n longitudinally
+/ p knot;
F. the aluminium back of the body (2) that uses conventional plasma chemical vapor deposition grown silicon nitride film and silk screen print method to prepare the argent gate line electrode (1) and the back side carries out high temperature sintering at last, forms selective emitter crystalline silicon solar cell.
2. according to the preparation method of a kind of selective emitter crystalline silicon solar cell of claim 1, it is characterized in that: said crystalline silicon comprises monocrystalline silicon and polysilicon.
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| FR2964252A1 (en) * | 2010-09-01 | 2012-03-02 | Commissariat Energie Atomique | Selective emitter structure i.e. photovoltaic cell, forming method, involves applying thermal energy on surface of substrate comprising temporary layer and residual zone, to simultaneously form final semiconductor layer and region |
| CN101950780B (en) * | 2010-09-09 | 2012-08-08 | 百力达太阳能股份有限公司 | Preparation method of selective emitter solar cell |
| CN101976708A (en) * | 2010-09-22 | 2011-02-16 | 中国科学院宁波材料技术与工程研究所 | Method for improving photoelectric conversion efficiency of crystal silicon solar battery |
| CN102637772B (en) * | 2012-03-28 | 2015-03-04 | 上饶光电高科技有限公司 | Method for preparing selective emitter of solar cell |
| CN102709391B (en) * | 2012-05-29 | 2016-04-27 | 上饶光电高科技有限公司 | A kind of preparation method of selective emitter solar battery |
| CN102769072B (en) * | 2012-07-31 | 2014-12-10 | 英利集团有限公司 | N-type crystalline silicon solar cell and preparation method thereof |
| CN102800757B (en) * | 2012-08-28 | 2016-03-16 | 英利集团有限公司 | N-type solar cell and manufacturing process thereof |
| CN102945892B (en) * | 2012-11-07 | 2015-08-05 | 南通大学 | A kind of method for manufacturing solar battery |
| US20140166094A1 (en) * | 2012-12-18 | 2014-06-19 | Paul Loscutoff | Solar cell emitter region fabrication using etch resistant film |
| CN103151428A (en) * | 2013-03-26 | 2013-06-12 | 浙江晶科能源有限公司 | Method for realizing selective emitter of crystalline silicon solar cell |
| CN103227238B (en) * | 2013-04-01 | 2015-11-18 | 林卓威 | A kind of production technology of monocrystaline silicon solar cell |
| CN103165761B (en) * | 2013-04-01 | 2015-07-01 | 南通大学 | Manufacturing method for solar cell |
| CN105140334B (en) * | 2013-04-01 | 2017-04-05 | 南通大学 | Solar cell selective doping method based on counter diffusion |
| CN103165760B (en) * | 2013-04-01 | 2015-08-05 | 南通大学 | A kind of selective doping method of solar cell |
| CN106449803A (en) * | 2016-12-16 | 2017-02-22 | 浙江晶科能源有限公司 | Manufacturing method of front surface electrode of silicon wafer |
| CN107256828A (en) * | 2017-05-16 | 2017-10-17 | 扬州晶新微电子有限公司 | A kind of phosphorosilicate glass annealing process for improving triode K values |
| CN112599636B (en) * | 2020-12-07 | 2023-08-01 | 浙江晶科能源有限公司 | Preparation method of crystalline silicon solar cell and crystalline silicon solar cell |
| CN115249750B (en) * | 2021-04-26 | 2023-08-11 | 浙江晶科能源有限公司 | Photovoltaic cell, manufacturing method thereof and photovoltaic module |
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| US20050172996A1 (en) * | 2004-02-05 | 2005-08-11 | Advent Solar, Inc. | Contact fabrication of emitter wrap-through back contact silicon solar cells |
| CN200962428Y (en) * | 2006-10-25 | 2007-10-17 | 宁波杉杉尤利卡太阳能科技发展有限公司 | N single crystal silicon solar battery of silk mesh printing aluminum back emission node |
| CN101369612A (en) * | 2008-10-10 | 2009-02-18 | 湖南大学 | Production method for implementing selective emitter solar battery |
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