CN108598219A - Optimize the wet method etch-back technics of black silicon emitter - Google Patents
Optimize the wet method etch-back technics of black silicon emitter Download PDFInfo
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- CN108598219A CN108598219A CN201810393484.9A CN201810393484A CN108598219A CN 108598219 A CN108598219 A CN 108598219A CN 201810393484 A CN201810393484 A CN 201810393484A CN 108598219 A CN108598219 A CN 108598219A
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- 238000000034 method Methods 0.000 title claims abstract description 63
- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000005457 optimization Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 9
- -1 nitrogenous organic base Chemical class 0.000 claims abstract description 9
- 238000007650 screen-printing Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 210000002268 wool Anatomy 0.000 claims description 6
- 235000008216 herbs Nutrition 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 3
- QQIRAVWVGBTHMJ-UHFFFAOYSA-N [dimethyl-(trimethylsilylamino)silyl]methane;lithium Chemical compound [Li].C[Si](C)(C)N[Si](C)(C)C QQIRAVWVGBTHMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 208000011117 substance-related disease Diseases 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000005360 phosphosilicate glass Substances 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical class N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a kind of wet method etch-back technics of the black silicon emitter of optimization, characterized in that uses following steps：The silicon chip for removing back side PSG is put into wet method eatch-back liquid, is handled 80 150 seconds in 40 80 DEG C；Wet method eatch-back liquid is using the mixing liquid of inorganic base or nitrogenous organic base substance and deaeration agent, and the mass percentage concentration of inorganic base or nitrogenous organic base substance is 1 5%, and the mass percentage concentration of deaeration agent is 0.01 0.05%.The present invention can promote the battery conversion efficiency of black silion cell, the problems such as solving silk-screen printing.
Description
Technical field
The present invention relates to a kind of wet method etch-back technics of the black silicon emitter of optimization, belong to field of photoelectric technology.
Background technology
In recent years, photovoltaic generation was the emerging environmental protection industry that country supports energetically.However its cost is too high, still can not
Replace traditional fossil energy.It is the key that realize the sustainable development of photovoltaic industry that drop, which originally puies forward effect,.Pass through casting ingot process, diamond wire
Silicon chip is cut, the cost of crystal silicon solar batteries is greatly reduced, realizes the large-scale production of photovoltaic generation.However, polycrystalline
The efficiency of solar cell still needs to further improve.
Black silicon is one of the route of current high-efficiency polycrystalline solar cell.In silicon wafer wool making, corroded by metal catalytic
100-1000 nanoscale hole holes are formed on polysilicon chip surface, further across the battery that rear road manufacturing procedure is prepared, quilt
Referred to as black silicon solar cell.Black silicon, with excellent anti-reflection effect, brings photoelectricity compared with conventional diamond wire battery
The opposite promotion of transfer efficiency 0.3%.Meanwhile black silicon is because of its unique making herbs into wool mode, the aberration caused by Buddha's warrior attendant wire cutting
Silicon chip surface making herbs into wool becomes solar cell industry and puies forward the effective means of effect drop originally.
To polysilicon solar cell, photoelectric conversion efficiency efficiency is improved, the P-N of " shallow junction is low-doped " should be formed as possible
Structure advantageously reduces the Carrier recombination of emitter.However as shown in Figure 1, black silicon making herbs into wool formation is a kind of nanoscale suede
Face, large specific surface area, the hole size that metal catalytic is formed and depth difference cause to be easy absorption high concentration in part when diffusion
Phosphorus doping source, and deeper hole can not spread or spread less, the uneven and heavily doped surface P-N junction of formation.It is this
There are larger parasitic recombination currents for P-N junction structure, and battery is prepared by conventional postchannel process, and opto-electronic conversion performance is relatively low,
The advantage of the excellent sunken light characteristic of black silicon nanometer suede can not be embodied.
More seriously, this nanometer-scale texture also has silk-screen printing great adverse effect, leads to silk-screen printing grid
The problems such as line easily breaks, pulling force is insufficient.Although the grain size and ratio by adjusting frit in slurry and Argent grain can improve
Printing issues, but result in that Schottky barrier is excessive, and cell series resistance is excessive, reduce black silion cell
Transfer efficiency.
Invention content
The purpose of the present invention is overcoming the deficiencies in the prior art, a kind of wet method time of the black silicon emitter of optimization is provided
The problems such as etching technique promotes the battery conversion efficiency of black silion cell, solves silk-screen printing.
According to technical solution provided by the invention, the wet method etch-back technics of the black silicon emitter of optimization, characterized in that adopt
Use following steps：
The silicon chip for removing back side PSG is put into wet method eatch-back liquid, is handled 80-150 seconds in 40-80 DEG C；The wet method is returned
Lose mixing liquid of the liquid using inorganic base or nitrogenous organic base substance and deaeration agent, inorganic base or nitrogenous organic base substance
Mass percentage concentration be 1-5%, the mass percentage concentration of deaeration agent is 0.01-0.05%.
Further, the inorganic base uses potassium hydroxide or sodium hydroxide.
Further, the nitrogenous organic base substance uses lithium diisopropyl amido or hexamethyldisilazane lithium.
Further, the deaeration agent is more than 5000 polymer alcohols using molecular weight.
Further, the deaeration agent uses polyethylene glycol, poly- butanol or isopropanol.
Further, the removal back side PSG is using hydrofluoric acid removal silicon chip back side PSG.
The present invention also provides a kind of battery production technologies of the black silicon emitter of optimization, characterized in that carries out black silicon system successively
Suede, normal pressure diffusion, removal silicon chip back side PSG, wet method etch-back technics, PECVD and silk-screen printing.
The present invention has the following advantages：
（1）The present invention can promote the battery conversion efficiency of black silion cell, the problems such as solving silk-screen printing；
（2）The heavily doped matte in part after the present invention goes except black silicon to spread by wet method eatch-back, optimization emitter uniform doping and
Junction depth improves doping concentration, its is more efficient for the black silion cell formed based on this technique plated film and silk screen；
（3）Wet method eatch-back of the present invention is compared with conventional batteries production line, without using there is the nitre greatly polluted to environment
The etch step of acid, and the inorganic base for being free from nitrogen or optional low nitrogen content organic base and easily biological-degradable alcohol
Class deaeration agent, chemicals cost is cheaper, and process route is more environmentally-friendly.
Description of the drawings
Fig. 1 is the black silicon nanometer suede scanning electron microscope diagram of metal catalytic corrosion.
Fig. 2 is that wet method is etched back method and conventional method technique battery partial structural diagram, and 1 is eatch-back method, and 2 be conventional method.
Fig. 3 is the battery production route map of usual processing route and wet method etch-back technics.
Fig. 4 is the ECV curve graphs of common process and wet method etch-back technics.
Specific implementation mode
With reference to specific attached drawing, the invention will be further described.
While the wet method etch-back technics of the black silicon emitter of optimization of the present invention can optimize front side of silicon wafer, to removal
PSG（Phospho Silicate Glass, phosphorosilicate glass）The back side directly polished.With conventional black silion cell production technology
Route is compared, backside reflection rate higher, and printing forms Al-BSF passivation effect and sunken luminous effect is more preferable, to more efficient.
As shown in figure 3, for the battery production route map of usual processing route and wet method etch-back technics, main difference is：Conventional silicon
PSG caused by being spread by acid etch removal after piece diffusion, and polished backside, further deposit passivating film and silk by front
Wire mark brush electrode is prepared into battery；And wet method etch-back technics is then the silicon chip removal back side PSG after spreading, and then puts silicon chip
Enter to wet method to be etched back in liquid and be reacted, while equally can be with polished backside, black silicon matte emitter be under the protection of PSG
By slight erosion in being etched back liquid, and other production stages are identical as regular course.As shown in Fig. 2, for wet method eatch-back and routine
The schematic diagram of emitter matte difference after route, wet method eatch-back are characterized in that removing the black silion cell of back side PSG after spreading
Piece is put into specific wet method eatch-back liquid, by controlling reaction time, temperature and eatch-back liquid concentration, after going except black silicon to spread
The heavily doped matte in part, optimizes emitter uniform doping and junction depth, improves doping concentration.Based on this technique plated film and silk screen
Its is more efficient for the black silion cell formed.
Embodiment 1：A kind of wet method etch-back technics of the black silicon emitter of optimization, using following steps：
Silicon chip back side PSG is removed using hydrofluoric acid, the silicon chip for removing back side PSG is put into wet method eatch-back liquid, in 60 DEG C
Processing 100 seconds；Wet method eatch-back liquid uses the mass percentage concentration to be for 1.5% sodium hydroxide and mass percentage concentration
The mixing liquid of 0.01% polyethylene glycol.
By the wet method etch-back technics of embodiment 1, silicon wafer suede pass is basically unchanged, and reflectivity remains unchanged, can by Fig. 4
Know, the surface dopant concentration of P-N junction is reduced to 2.96E+20 cm by 5.92E+20-3, junction depth is reduced to 0.25 micro- by 0.28 micron
Rice, and then its average photoelectric conversion efficiency is improved by 19.05% to 19.2% or more.
Embodiment 2：A kind of wet method etch-back technics of the black silicon emitter of optimization, using following steps：
Silicon chip back side PSG is removed using hydrofluoric acid, the silicon chip for removing back side PSG is put into wet method eatch-back liquid, in 40 DEG C
Processing 150 seconds；It for 1% potassium hydroxide and mass percentage concentration is 0.02% that wet method eatch-back liquid, which uses mass percentage concentration,
Poly- butanol.
The heavily doped matte in part, optimizes emitter uniform doping and junction depth after the present embodiment can go except black silicon to spread,
Improve doping concentration.Its more efficient, silicon handled through embodiment 2 of black silion cell based on this technique plated film and silk screen formation
Piece be averaged photoelectric conversion efficiency promoted 0.05%.
Embodiment 3：A kind of wet method etch-back technics of the black silicon emitter of optimization, using following steps：
Silicon chip back side PSG is removed using hydrofluoric acid, the silicon chip for removing back side PSG is put into wet method eatch-back liquid, in 80 DEG C
Processing 80 seconds；The wet method eatch-back liquid uses lithium diisopropyl amido and mass percentage concentration of the mass percentage concentration for 1.2%
For 0.05% isopropanol.
The heavily doped matte in part, optimizes emitter uniform doping and junction depth after the present embodiment can go except black silicon to spread,
Improve doping concentration.Its more efficient, silicon handled through embodiment 2 of black silion cell based on this technique plated film and silk screen formation
Piece be averaged photoelectric conversion efficiency promoted 0.08%.
Embodiment 4：
A kind of battery production technology of the black silicon emitter of optimization, carries out black silicon making herbs into wool, normal pressure diffusion, removal silicon chip back side successively
PSG, wet method etch-back technics, PECVD and silk-screen printing；Wherein, the wet method etch-back technics uses following steps：
Silicon chip back side PSG is removed using hydrofluoric acid, the silicon chip for removing back side PSG is put into wet method eatch-back liquid, in 60 DEG C
Processing 100 seconds；Wet method eatch-back liquid uses the mass percentage concentration to be for 1.5% sodium hydroxide and mass percentage concentration
The mixing liquid of 0.01% polyethylene glycol；
By the above process to realize the adjustment of silicon wafer suede, and then surface concentration and junction depth are reduced, average photoelectric efficiency is opposite
Common process has at least 0.05% promotion.
The present invention eliminates local heavily doped matte after black silicon diffusion, it is low can to form shallow junction by wet method etch-back technics
The P-N junction emitter of doping, significantly reduces the Carrier recombination of emitter；Meanwhile be conducive to hydrogenated silicon nitride deposition and
Passivation, improves the press quality and pulling force of the positive silver grating line of silk screen.The present invention is promoting the battery conversion efficiency of black silion cell
Meanwhile, it is capable to which the problems such as solving silk-screen printing, is suitable for the production of the black silion cell of high-efficiency polycrystalline；Meanwhile being based on wet method eatch-back side
The production cost of the solar cell of method is lower, more efficient.
Claims (7)
1. a kind of wet method etch-back technics of the black silicon emitter of optimization, characterized in that use following steps：
The silicon chip for removing back side PSG is put into wet method eatch-back liquid, is handled 80-150 seconds in 40-80 DEG C；The wet method is returned
Lose mixing liquid of the liquid using inorganic base or nitrogenous organic base substance and deaeration agent, inorganic base or nitrogenous organic base substance
Mass percentage concentration be 1-5%, the mass percentage concentration of deaeration agent is 0.01-0.05%.
2. optimize the wet method etch-back technics of black silicon emitter as described in claim 1, it is characterized in that：The inorganic base uses hydrogen
Potassium oxide or sodium hydroxide.
3. optimize the wet method etch-back technics of black silicon emitter as described in claim 1, it is characterized in that：The nitrogenous organic base
Substance uses lithium diisopropyl amido or hexamethyldisilazane lithium.
4. optimize the wet method etch-back technics of black silicon emitter as described in claim 1, it is characterized in that：The deaeration agent, which uses, to divide
Polymer alcohols of the son amount more than 5000.
5. optimize the wet method etch-back technics of black silicon emitter as described in claim 1, it is characterized in that：The deaeration agent is using poly-
Ethylene glycol, poly- butanol or isopropanol.
6. optimize the wet method etch-back technics of black silicon emitter as described in claim 1, it is characterized in that：The removal back side PSG
Using hydrofluoric acid removal silicon chip back side PSG.
7. a kind of battery production technology of the black silicon emitter of optimization, characterized in that carry out black silicon making herbs into wool successively, normal pressure diffusion, go
Except silicon chip back side PSG, wet method etch-back technics, PECVD and silk-screen printing.
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| CN201810393484.9A CN108598219A (en) | 2018-04-27 | 2018-04-27 | Optimize the wet method etch-back technics of black silicon emitter |
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| CN201810393484.9A CN108598219A (en) | 2018-04-27 | 2018-04-27 | Optimize the wet method etch-back technics of black silicon emitter |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120181502A1 (en) * | 2011-01-18 | 2012-07-19 | Bandgap Engineering, Inc. | Method of electrically contacting nanowire arrays |
| CN104934500A (en) * | 2015-05-18 | 2015-09-23 | 润峰电力有限公司 | Method for preparing back-surface passivation crystalline silicon solar cell with selective emitter |
| CN107919275A (en) * | 2017-11-16 | 2018-04-17 | 北京普扬科技有限公司 | A kind of silicon chip that room temperature etching method and its making herbs into wool form, solar battery sheet and preparation method thereof |
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2018
- 2018-04-27 CN CN201810393484.9A patent/CN108598219A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120181502A1 (en) * | 2011-01-18 | 2012-07-19 | Bandgap Engineering, Inc. | Method of electrically contacting nanowire arrays |
| CN104934500A (en) * | 2015-05-18 | 2015-09-23 | 润峰电力有限公司 | Method for preparing back-surface passivation crystalline silicon solar cell with selective emitter |
| CN107919275A (en) * | 2017-11-16 | 2018-04-17 | 北京普扬科技有限公司 | A kind of silicon chip that room temperature etching method and its making herbs into wool form, solar battery sheet and preparation method thereof |
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| CN108598219A (en) | Optimize the wet method etch-back technics of black silicon emitter |
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Application publication date: 20180928 |