CN105489708B - A kind of p-type silicon solar cell and preparation method thereof - Google Patents
A kind of p-type silicon solar cell and preparation method thereof Download PDFInfo
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- CN105489708B CN105489708B CN201610030388.9A CN201610030388A CN105489708B CN 105489708 B CN105489708 B CN 105489708B CN 201610030388 A CN201610030388 A CN 201610030388A CN 105489708 B CN105489708 B CN 105489708B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 129
- 239000010703 silicon Substances 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000002161 passivation Methods 0.000 claims abstract description 86
- 239000000758 substrate Substances 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 238000007639 printing Methods 0.000 claims abstract description 13
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 31
- 230000010287 polarization Effects 0.000 claims description 16
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 9
- 235000008216 herbs Nutrition 0.000 claims description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 8
- 210000002268 wool Anatomy 0.000 claims description 8
- 229910002113 barium titanate Inorganic materials 0.000 claims description 7
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910000859 α-Fe Inorganic materials 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 238000003475 lamination Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229910017083 AlN Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 34
- 230000000694 effects Effects 0.000 description 10
- 239000002002 slurry Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 229910004205 SiNX Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006388 chemical passivation reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000000608 laser ablation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
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- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
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- 230000003628 erosive effect Effects 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
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- 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
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- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
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- 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
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Abstract
The invention provides a kind of p-type silicon solar cell and preparation method thereof.The p-type silicon solar cell includes p-type silicon substrate, and n is formed with the front of p-type silicon substrate+Doped layer and antireflection layer, front electrode, front electrode and n are formed with through the antireflection layer+Doped layer connects；Backside passivation layer is formed with the back side of the p-type silicon substrate, the backside passivation layer includes the film layer made of ferroelectric thin-flim materials or the ferroelectric thin-flim materials of doping, is overleaf formed with backplate by printing, sintering process on passivation layer.The present invention uses main material of the ferroelectric thin-flim materials as cell backside passivation layer, can improve the open-circuit voltage and short circuit current of battery well, improve the conversion efficiency of battery.
Description
Technical field
The present invention relates to technical field of solar batteries, specifically a kind of p-type silicon solar cell and its preparation side
Method.
Background technology
The surface defect of crystal silicon solar energy battery has very big influence, the open-circuit voltage of battery to battery performance
（Voc）, short circuit current（Jsc）, fill factor, curve factor（FF）The height of surface defect density is largely dependent upon Deng major parameter.
The recombination losses of photo-generated carrier are one of main paths of solar battery efficiency loss, and surface recombination is most important multiple
Close loss.Surface defect density is reduced, reduces surface recombination, is the important hand for improving silicon solar cell energy conversion efficiency
Section.Passivation can effectively reduce the compound of carrier, and then improve the conversion efficiency of solar cell.Passivation generally has chemical passivation
Two methods are passivated with field.Chemical passivation is typically that passivating material chemically reacts with silicon chip surface, bonding, and then reduces table
Face silicon dangling bond, reach the purpose of passivation；Field passivation refers to drive silicon using Coulombian field caused by the charged ion in passivating material
The electronics of piece near surface or hole make it away from surface and then reduce their surface recombination, so as to realize the effect of passivation.
Passivation layer is usually made using passivating material in the front and back of battery in the prior art, to reduce surface
Defect concentration；And the coated with antireflection film on the passivation layer of front, the positive surface charge of screen printing electrode slurry collection, is overleaf passivated
Printed on layer after local openings untouchable electrode slurry or using physical vaporous deposition prepare full back of the body metal electrode to
Collect back side electric charge.Existing frequently-used passivating material includes SiO2（Silica, abbreviation silica）、SiNx（Silicon nitride, also may be used
Write Si3N4）、Al2O3（Alundum (Al2O3), abbreviation aluminum oxide）、a-Si:H（Amorphous silicon hydride）Or they be combined with each other it is folded
Layer.Wherein SiO2It is typical chemical passivation material, there is extraordinary passivation effect, but need about 800-900 DEG C of height
Warm technique, which carries out thermal oxide, can be just prepared, and the impurity and defect on inside silicon chip and surface are seriously have impact on while power consumption.
a-Si:H also has good passivation effect, but its preparation technology requirement is less than 200 DEG C, with diffusion junctions crystal silicon cell industry
Chemical industry skill is incompatible, is not ordinarily considered for the surface passivation of diffusion junctions crystal silicon cell.SiNxAnd Al2O3It is blunt based on field
The principle of change, i.e. SiNxContain fixed positive charge, Al in inside2O3Containing negative electrical charge, it is respectively suitable for being passivated n-type and p-type silicon table
Face, it is with certain passivation effect and compatible with industry, but both materials are all good dielectric materials, are had very
The charge-conduction ability of difference, thus in silicon solar cell is integrated into after, it is necessary to lbg, form metal electrode and silicon
Localized contact and local passivation, while increase process complexity is with cost is prepared, inevitably reduce solar cell
Fill factor, curve factor, limit the further lifting of efficiency.Further, after lbg, in order to form localized contact, it is necessary to there is selection
Property print untouchable electric slurry, this will require that printing machine has accurately technique of alignment（Increase cost）, while to disappear
Consume slurry（Slurry occupies most of cost in crystal silicon solar energy battery preparation process）, this is all unfavorable for the development of technology.
The content of the invention
An object of the present invention is just to provide a kind of p-type silicon solar cell, to solve existing p-type silicon solar-electricity
The problem of pond conversion efficiency is low.
The second object of the present invention is just to provide a kind of preparation method of p-type silicon solar cell, and the preparation method can adopt
The higher p-type silicon solar cell of efficiency is prepared with relatively low manufacturing cost.
What an object of the present invention was realized in：A kind of p-type silicon solar cell, including p-type silicon substrate, described
The front of p-type silicon substrate is formed with n by diffusion technique or ion implantation technology etc.+Doped layer, in the n+It is formed with and subtracts on doped layer
Reflecting layer；Front electrode is formed with by printing, sintering process on the antireflection layer, the front electrode passes through the anti-reflection
Penetrate layer and the n+Doped layer connects；Backside passivation layer is formed with the back side of the p-type silicon substrate, the backside passivation layer includes
The film layer made of ferroelectric thin-flim materials or the ferroelectric thin-flim materials of doping, by printing, sintering in the backside passivation layer
Technique is formed with backplate.
The backside passivation layer is included in lead zirconate titanate film layer, bismuth ferrite film layer, barium titanate film layer and barium strontium titanate film layer
One kind or any two kinds of laminations be combineding with each other.
The backside passivation layer also includes the film layer made of aluminum oxide and/or silicon nitride material.
The thickness of the backside passivation layer is 3nm ~ 600nm.
Coverage rate of the backside passivation layer at the p-type silicon substrate back side is 5% ~ 100%.
The p-type silicon substrate is monocrystalline or Multicrystalline p-type silicon substrate.
P-type silicon solar cell provided by the present invention, n is sequentially formed with the front of p-type silicon substrate+Doped layer and subtract
Reflecting layer, backside passivation layer is formed with the back side of p-type silicon substrate, and backside passivation layer includes the iron by ferroelectric thin-flim materials or doping
Film layer made of conductive film material, ferroelectric thin-flim materials exist certainly as a kind of functional oxide thin-film material because it is internal
Polarization field is sent out, therefore is applied to the back surface of crystal silicon solar energy battery as main passivating material, can very great Cheng
The life-span of photo-generated carrier is improved on degree, lifts the open-circuit voltage of battery；In addition, passivating back is made using ferroelectric thin-flim materials
Layer, it can also strengthen the back reflection of silicon solar cell in addition to the effect for possessing passivation effect, and this largely improves
The short circuit current of solar cell；Natural localized contact is formd between backside passivation layer and p-type silicon substrate, is avoided completely
The use of the complicated technologies such as laser ablation, fluting, which strongly simplifies technique, reduce being manufactured into for solar cell
This, while ensure that the lifting of battery efficiency.Traditional PERC（Passivated Emitter and Rear Cell, passivation hair
The She Qu back sides）In battery, because there is Al2O3Use, Si and passivation layer interface charge density are reduced under illumination, cause to be passivated matter
Amount declines, and produces light-induced degradation（LID）Effect.The present invention uses ferroelectric thin-flim materials（Such as PZT）As passivation layer, passivation mechanisms
Polarization field is come from, therefore this problem can be avoided, reduces LID effects.
What the second object of the present invention was realized in：A kind of preparation method of p-type silicon solar cell, including following step
Suddenly：
A, choose p-type silicon substrate, the p-type silicon substrate is cleaned and front, back side making herbs into wool；
B, n is made by doping in the front of the p-type silicon substrate+Doped layer, and the edge of p-type silicon substrate is carved
Erosion；
C, in the n+Antireflection layer is prepared on doped layer；
D, backside passivation layer is prepared at the back side of the p-type silicon substrate, and is moved back under conditions of being 450 DEG C ~ 700 DEG C in temperature
Fire processing 1min ~ 90min, the backside passivation layer include the film made of ferroelectric thin-flim materials or the ferroelectric thin-flim materials of doping
Layer；
E, front electrode is prepared by printing, sintering process, the front electrode passes through the antireflection layer and the n+
Doped layer connects；
F, backplate is prepared in the backside passivation layer by printing, sintering process；
G, the p-type silicon solar cell of above-mentioned preparation is polarized, specific polarization process is：Using voltage-stabilized power supply to upper
The p-type silicon solar cell for stating preparation applies a constant voltage or constant current, and constant voltage scope is 1V ~ 50V, constant current
Scope is 0.01A ~ 10A, and the polarization time is 1s ~ 100s.
P-type silicon substrate described in step a is monocrystalline p-type silicon substrate；And also include before step b after step a as follows
Step：Planarization process is carried out to the back side of the p-type silicon substrate.
Backside passivation layer formed in step d includes lead zirconate titanate film layer, bismuth ferrite film layer, barium titanate film layer and metatitanic acid
One kind or any two kinds of laminations be combineding with each other in strontium barium film layer.
The thickness of backside passivation layer formed in step d is 3nm ~ 600nm.
The preparation method of p-type silicon solar cell provided by the present invention, in the front of silicon substrate according to existing process system
Standby n+Doped layer and antireflection layer, pass through sol-gel process at the back side of silicon substrate（sol-gel）, physical vaporous deposition
（PVD）, chemical vapour deposition technique（CVD）Or pulse laser deposition（PLD）Deng preparation backside passivation layer, and to backside passivation layer
Being made annealing treatment, backside passivation layer includes the film layer made of ferroelectric thin-flim materials or the ferroelectric thin-flim materials of doping, such as
Backside passivation layer includes lead zirconate titanate（PZT）Film layer, barium titanate（BaTiO3, it is abbreviated as BTO）Film layer, bismuth ferrite（BFO）Film layer
Or barium strontium titanate（BST）Film layer, it can also be any two or three shape that be combined with each other in PZT, BTO, BFO and bst film layer
Into lamination, can also be doping（Such as doping La or Ni etc.）PZT, BTO, BFO or bst film layer etc..Prior art uses
Aluminum oxide or silicon nitride passivation layer material, operation principle be based on coulomb electrostatic field caused by the fixed charge of material internal,
Main material of the ferroelectric thin-flim materials of the present invention as backside passivation layer, it is that the ferroelectricity based on ferroelectric thin-flim materials is special
There is polarization field in property, i.e. material internal, the generation root of polarization field is due to the special structure of ferroelectric thin-flim materials, i.e. perovskite
Structure, in perovskite structure, electric dipole moment is formed because positive and negative charge center is misaligned, polarization is produced in material internal
, this is the special physical mechanism of this kind of material, is applied to the back side of crystal silicon solar energy battery as passivating material,
The open-circuit voltage, short circuit current and fill factor, curve factor of battery can be improved well, embody excellent passivation effect.Moreover,
After preparing front electrode and backplate, p-type silicon solar cell is polarized using voltage-stabilized power supply, battery after polarization
FF will be improved significantly, further improve the energy conversion efficiency of battery.
Brief description of the drawings
Fig. 1 is the structural representation of p-type silicon solar cell in the present invention.
Fig. 2 is the SEM figures of silicon substrate back surface after formation PZT backside passivation layers in the embodiment of the present invention 2.
Fig. 3 is the XRD test charts of p-type silicon solar cell prepared in the embodiment of the present invention 2.
Fig. 4 is that the quantum efficiency curve for the p-type silicon solar cell that the embodiment of the present invention 2 and comparative example 1 are prepared respectively shows
It is intended to.
Embodiment
Embodiment 1, a kind of p-type silicon solar cell.
As shown in figure 1, the p-type silicon solar cell that the present embodiment is provided includes p-type silicon substrate 4, p-type silicon substrate 4 can
Think monocrystalline p-type silicon substrate or Multicrystalline p-type silicon substrate.Pass through diffusion technique or ion in the front of p-type silicon substrate 4
Injection technology etc. is formed with n+Doped layer 3, in n+Antireflection layer 2 is formed with doped layer 3, on antireflection layer 2 by silk-screen printing,
Sintering process is formed with front electrode 1, and front electrode 1 can pass through antireflection layer 2 and n after sintering+Doped layer 3 connects.
Backside passivation layer 5 is formed with the back side of p-type silicon substrate 4, the main material of backside passivation layer 5 is ferroelectric thin membrane material
Material, ferroelectric thin-flim materials for example can be lead zirconate titanate（PZT）, barium titanate（BTO）, bismuth ferrite（BFO）Or barium strontium titanate
（BST）Deng can be with doping inside ferroelectric thin-flim materials（Such as mix La or Ni etc.）.Backside passivation layer 5 can be PZT film
Layer, BTO film layers, BFO film layers or bst film layer, can also in above-mentioned film layer doping, can also be any in above-mentioned film layer
Two or more film layer is together with each other the laminated construction to be formed.In addition, backside passivation layer 5 can also include
The film layer made of aluminum oxide and/or silicon nitride passivation material, i.e.,：The film made of aluminum oxide and/or silicon nitride passivation material
Layer with by ferroelectric thin-flim materials or doping ferroelectric thin-flim materials made of film layer be bound to each other to form laminated construction, collectively constitute the back of the body
Face passivation layer.Backside passivation layer 5 can pass through sol-gel process（sol-gel）To prepare, physical vapour deposition (PVD) can also be passed through
Method（PVD）, chemical vapour deposition technique（CVD）Or pulse laser deposition（PLD）The methods of prepare.The thickness of backside passivation layer 5
It can be controlled between 3nm ~ 600nm.Coverage rate of the backside passivation layer 5 at the back side of p-type silicon substrate 4 can be 5% ~ 100%, i.e.,：The back of the body
The back side of p-type silicon substrate 4 can be completely covered in face passivation layer 5, can also a back side of blanket p-type silicon substrate 4 subregion.Carrying on the back
Backplate 6 is formed with by printing, sintering process on face passivation layer 5.
Embodiment 2, a kind of preparation method of p-type silicon solar cell.
The preparation method for the p-type silicon solar cell that the present embodiment is provided comprises the following steps：
1., choose p-type silicon substrate, and selected p-type silicon substrate is cleaned, to the front of p-type silicon substrate after cleaning
Distinguish making herbs into wool with the back side.P-type silicon substrate can be monocrystalline p-type silicon substrate or Multicrystalline p-type silicon substrate.When it is monocrystalline p
During type silicon substrate, making herbs into wool is typically carried out to it using alkali, ultimately forms regular pyramid light trapping structure.When it is Multicrystalline p-type
It is general that making herbs into wool is carried out to it using acid during silicon substrate, ultimately form regular rough hole shape surface light trapping structure.This reality
It is monocrystalline p-type silicon substrate to apply p-type silicon substrate in example, and the pyramidal average height formed after making herbs into wool is 1 μm ~ 15 μm.
2., the front of p-type silicon substrate using phosphorus diffusion formed heavy doping n+Doped layer, etching edge is carried out afterwards,
Remove the doped layer at edge.
3., in n+Antireflection layer is prepared on doped layer, antireflection layer is silicon nitride in the present embodiment（SiNx）Film layer, the nitrogen
SiClx film layer also has passivation, can also regard positive passivation layer.
4., p-type silicon substrate the back side prepare PZT backside passivation layers.Specifically：Choose Pb1.15(Zr0.4Ti0.6)O3Forerunner
Liquid solution（There is 15% excessive Pb）, to avoid, because Pb volatilizees in high temperature oxygen atmosphere processing procedure, causing PZT to lack lead and influence
Pzt thin film performance；Realize that lead zirconate titanate precursor solution is coated on the back side of p-type silicon substrate using desk-top sol evenning machine：First with
500 revs/min of speed rotates 6 seconds, is then rotated 40 seconds at a high speed by 4000 revs/min.Using board-like stove, after spin coating
Wet film is 200oToasted 5 minutes under C, decompose organic matter, volatilization.General control backside passivation layer is at the p-type silicon substrate back side
Coverage rate is 5% ~ 100%, and the thickness for controlling backside passivation layer is 3nm ~ 600nm.Backside passivation layer all covers p in the present embodiment
The type silicon substrate back side, and the thickness of backside passivation layer is 200nm.
5., the silicon substrate that will scribble PZT backside passivation layers carry out short annealing, annealing temperature is 450-700 DEG C, during annealing
Between be 1min ~ 90min.
Electronic Speculum test is scanned to the silicon substrate back side after PZT backside passivation layers are formed, acquired results are shown in Fig. 2.In Fig. 2
（a）For ESEM exterior view,（b）For ESEM sectional drawing, it can be seen that big pyramid or medium size
Pyramidal tower top does not have pzt thin film distribution, and the bottom of pyramidion and Great Pyramid has been covered with pzt thin film, therefore, adopts
Natural localized contact can with wonderful workmanship excelling nature be formed with the method for the present invention, it is entirely avoided post laser ablation, fluting etc.
The use of complicated technology, simplify the performance boost that battery is ensure that while technique reduces cost.
6., pass through printing（Or evaporation）Technique printed electronic slurry, is sintered afterwards, forms front electrode；After sintering
Electric slurry penetrate silicon nitride antireflection layer and n naturally+Doped layer connects.Ag slurries are chosen when prepared by front electrode.
7., by typography printed electronic slurry, be sintered afterwards, form backplate, backplate is covered in
The whole back side of silicon substrate.After step 5. middle formation PZT backside passivation layers, big pyramid or medium size pyramid
Tower top there is no pzt thin film distribution, therefore, natural office is formd between the backplate and silicon substrate formed in this step
Portion contacts, without carrying out the techniques such as laser ablation, fluting again.Al slurries are chosen when prepared by backplate.
8., the p-type silicon solar cell of above-mentioned preparation is polarized.This step is one of features of the present invention.
The polarization field of ferroelectric thin-flim materials can change with the change of extra electric field, and this is that it is different from general passivation material
Expect most significant feature.Therefore it is constant one to be applied to the p-type silicon solar cell of above-mentioned preparation using voltage-stabilized power supply in this step
Voltage or constant current, constant voltage scope are 1V ~ 50V, and constant current range is 0.01A ~ 10A, the polarization time be 1s ~
100s.Used in the present embodiment is 5V DC voltage.
The present invention to p-type silicon solar cell by polarizing, thus it is possible to vary the photovoltaic performance of battery, battery after polarization
Photovoltaic performance substantially improved.
X-ray diffraction test is carried out to the p-type silicon solar cell after the polarization prepared by the present embodiment, acquired results are shown in
Fig. 3, as seen from Figure 3 PZT some characteristic peaks, show that PZT material has good polycrystalline perovskite structure in battery.
Comparative example 1
Compared with Example 2, p-type silicon solar cell prepared in this comparative example does not have PZT backside passivation layers, i.e.,：
This comparative example include embodiment 2 in step 1., 2., 3., 6. and 7., without step 4., 5. and 8..
It is close that open-circuit voltage, short circuit current are carried out respectively to the p-type silicon solar cell prepared by this comparative example and embodiment 2
The test of degree, fill factor, curve factor and efficiency, acquired results are shown in Table 1.
Table 1
As seen from Table 1, the back side prepares the battery after PZT passivation layers compared with the battery without PZT, open-circuit voltage and short circuit
Electric current is obviously improved, and fill factor, curve factor does not influence cell power conversion efficiency because localized contact can be reduced slightly
Lifting.It can be seen that set the silicon solar cell of PZT backside passivation layers increases than the absolute magnitude that the battery efficiency without PZT has 1%.
Quantum efficiency test is carried out to the p-type silicon solar cell prepared by this comparative example, while to prepared by embodiment 2
P-type silicon solar cell carry out quantum efficiency test, acquired results are shown in Fig. 4, as seen from Figure 4, the solar energy after PZT passivation
Battery, compared to the solar cell without PZT, there is more preferable long-wave response.
For solar cell after PZT is passivated is compared without PZT solar cell, silicon solar can be strengthened by also having
The advantages of battery back reflection, moreover, the introducing of PZT backside passivation layers can lift the life-span of inside battery photo-generated carrier, hence it is evident that
Improve the photovoltaic performance of battery.
Embodiment 3
Compared with Example 2, the present embodiment step 1. after, step 2. before add step：To p-type silicon substrate
The back side carries out planarization process.In the present embodiment the step of increase " carrying out planarization process to the back side of p-type silicon substrate ", its mesh
Be in order to be the somewhat smooth back side by the back side process of pyramid shape, i.e.,：By pyramidal top apex smoothing processing, make
The sharp angled construction of tower top pointed structures and the lowest point of pyramid structure becomes round and smooth, while cause pyramid surface by thick
It is rough to become relative smooth.After back side progress planarization process to p-type silicon substrate, it should ensure that and be subsequently formed after backside passivation layer still
Natural localized contact can be so formed, is so easy to prepare backplate subsequently through printing, sintering process.
Planarization process is carried out after making herbs into wool to the back side of p-type silicon substrate in the present embodiment, can further improve the back side
Passivation effect, increase internal reflection rate, improve short circuit current.
Claims (6)
1. a kind of p-type silicon solar cell, it is characterized in that, including p-type silicon substrate, in the front and back of the p-type silicon substrate
The suede structure of pyramid shape is formed with, and pyramidal average height is controlled between 1 μm ~ 15 μm in suede structure；Institute
The front for stating p-type silicon substrate is formed with n+Doped layer, in the n+Antireflection layer is formed with doped layer；Lead on the antireflection layer
Cross printing, sintering process is formed with front electrode, the front electrode is through the antireflection layer and the n+Doped layer connects；
The back side of the p-type silicon substrate is formed with backside passivation layer by spin coating proceeding, and the backside passivation layer is included by ferroelectric thin membrane material
Film layer made of material or the ferroelectric thin-flim materials of doping, specifically, the backside passivation layer includes lead zirconate titanate film layer, bismuth ferrite
Film layer, barium titanate film layer and one kind in barium strontium titanate film layer or any two kinds of laminations be combineding with each other；The backside passivation layer
Thickness be 3nm ~ 600nm；Backplate is formed with by printing, sintering process in the backside passivation layer；The p-type silicon is too
Positive energy battery is the solar cell after voltage-stabilized power supply polarizes, and specific polarization process is：Using voltage-stabilized power supply to the p-type silicon sun
It is 1V ~ 50V that energy battery, which applies a constant voltage or constant current, constant voltage scope, and constant current range is 0.01A ~ 10A,
Polarization time is 1s ~ 100s.
2. p-type silicon solar cell according to claim 1, it is characterized in that, the backside passivation layer also includes by aoxidizing
Film layer made of aluminium and/or silicon nitride material.
3. p-type silicon solar cell according to claim 1, it is characterized in that, the backside passivation layer is carried on the back in p-type silicon substrate
The coverage rate in face is 5% ~ 100%.
4. p-type silicon solar cell according to claim 1, it is characterized in that, the p-type silicon substrate is monocrystalline or polycrystalline p
Type silicon substrate.
5. a kind of preparation method of p-type silicon solar cell, it is characterized in that, comprise the following steps：
A, choose p-type silicon substrate, the p-type silicon substrate is cleaned and front, back side making herbs into wool；In p-type silicon substrate after making herbs into wool
Front and back form the suede structure of pyramid shape, and in suede structure the control of pyramidal average height at 1 μm ~ 15 μm
Between；
B, n is made by doping in the front of the p-type silicon substrate+Doped layer, and the edge of p-type silicon substrate is performed etching；
C, in the n+Antireflection layer is prepared on doped layer；
D, backside passivation layer is prepared by spin coating proceeding at the back side of the p-type silicon substrate, and is 450 DEG C ~ 700 DEG C in temperature
Under the conditions of make annealing treatment 1min ~ 90min, the backside passivation layer include by ferroelectric thin-flim materials or doping ferroelectric thin-flim materials
Manufactured film layer；Specifically, the backside passivation layer includes lead zirconate titanate film layer, bismuth ferrite film layer, barium titanate film layer and metatitanic acid
One kind or any two kinds of laminations be combineding with each other in strontium barium film layer；The thickness of the backside passivation layer is 3nm ~ 600nm；
E, front electrode is prepared by printing, sintering process, the front electrode passes through the antireflection layer and the n+Doped layer
Connect；
F, backplate is prepared in the backside passivation layer by printing, sintering process；
G, the p-type silicon solar cell of above-mentioned preparation is polarized, specific polarization process is：Using voltage-stabilized power supply to above-mentioned system
Standby p-type silicon solar cell applies a constant voltage or constant current, and constant voltage scope is 1V ~ 50V, constant current range
For 0.01A ~ 10A, the polarization time is 1s ~ 100s.
6. the preparation method of p-type silicon solar cell according to claim 5, it is characterized in that, p-type silicon described in step a
Substrate is monocrystalline p-type silicon substrate；And also comprise the following steps before step b after step a：To the back of the body of the p-type silicon substrate
Face carries out planarization process.
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| CN102339902A (en) * | 2011-07-30 | 2012-02-01 | 常州天合光能有限公司 | Method for making p-type solar battery by mask diffusion method and structure of p-type solar battery |
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