CN104064623A - Post-treatment method for increasing conversion efficiency of solar cell - Google Patents
Post-treatment method for increasing conversion efficiency of solar cell Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 68
- 238000002360 preparation method Methods 0.000 claims abstract description 41
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 36
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- 239000002243 precursor Substances 0.000 claims abstract description 31
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 31
- 238000000137 annealing Methods 0.000 claims abstract description 26
- 230000008021 deposition Effects 0.000 claims abstract description 25
- 238000004140 cleaning Methods 0.000 claims abstract description 24
- 238000009792 diffusion process Methods 0.000 claims abstract description 24
- 238000012360 testing method Methods 0.000 claims abstract description 18
- 238000005507 spraying Methods 0.000 claims abstract description 14
- 238000007650 screen-printing Methods 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 239000006117 anti-reflective coating Substances 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 20
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000013459 approach Methods 0.000 claims description 16
- 238000012805 post-processing Methods 0.000 claims description 16
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- 238000012958 reprocessing Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 235000008216 herbs Nutrition 0.000 claims description 10
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 48
- 230000000694 effects Effects 0.000 description 34
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- 238000002310 reflectometry Methods 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000011712 cell development Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
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- 238000009713 electroplating Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
-
- 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
-
- 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)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Energy (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a post-treatment method for increasing the conversion efficiency of a solar cell. The post-treatment method comprises the steps of taking the prepared solar cell as a substrate, and carrying out a post-treatment process on the front surface of the prepared solar cell; the realization flow is divided into two phases as a whole: the first phase is a conventional solar cell preparation flow: texturing, cleaning and drying, high-temperature diffusion, secondary cleaning, silicon nitride deposition, silk-screen printing and sintering test, and the second phase is a post-treatment process: precursor solution deposition and drying, and an annealing test. According to the post-treatment method disclosed by the invention, silicon oxide precursor solution is deposited on the front surface of the solar cell substrate by a spray-coating method, and a silicon oxide film layer is formed after drying and annealing, so as to obtain a 'silicon oxide/silicon nitride' double-layer antireflection film.
Description
Technical field
The present invention relates to a kind of solar cell, especially the post-processing approach of crystal-silicon solar cell.
Background technology
Solar cell development, the main task of producing are to reduce costs, and improve conversion efficiency, and guarantee the stability in use procedure.Reduce costs and can replace by material (Yehua Tang, Chunlan Zhou, Wenjing Wang, et.al., Solar Energy, Vol.95, mode 2013:265-270) realizes, conversion efficiency promotes multiple implementation, comprise and reduce surface reflectivity (Yehua Tang, Chunlan Zhou, Su Zhou, et.al., Chinese Journal of Chemical Physics, Vol.26 (1), 2013:102-108), battery structure improves (CAS Electrical Engineering Research Institute, the method of a kind of boron (B) diffusing, doping, 201210301219.6) and device structure transformation (CAS Electrical Engineering Research Institute, a kind of diffusion furnace fire door backflow parts, 201210073355.4).With regard to solar cell stability in use, voltage induction decay (Potential Induced Degradation:PID) effect becomes one of hot issue of current extensive concern.Solar cell is in running, and system voltage makes to have formed a back bias voltage between frame and cell piece, causes assembly power output to reduce, and this power attenuation phenomenon causing due to bias voltage induction is called voltage induction decay (being PID) effect.Bias voltage size depends on array quantity, inverter style and assembly residing position in array, be arranged on the bias value that the solar panel of diverse location in array forms different, cause electric leakage in various degree, so the degree of PID effects is also different.
In order to slow down the impact of PID effect, from modular construction, design again, install the aspects such as monitoring and auxiliary material improvement in performance and set about really can realizing the alleviation of PID effect, however and cannot be from eliminating in essence the impact of PID effect.People once thought, solar cell production process and technological process change can not affect solar cell application, yet situation is just in time contrary.Solar cell piece is the elementary cell of photovoltaic module application, and it prepares the stability that each flow process, step, technological parameter and material therefor etc. use assembly vital effect, can impact component application.Solar module forces the sodium in glass to form cation under high bias voltage, sodium ion free movement is spread to solar battery surface through packaging adhesive film, silicon nitride film layer at solar battery surface is assembled (V.Naumann, C.Hagendorf, S.Grosser, M.Werner, J.Bagdahn, Energy Procedia, Proceedings of the2
ndinternational conference on crystalline silicon photovoltaics silicon PV2012, Vol.27, 2012:1-6), formed electric field and solar cell emitter interface electric field mutually superpose and weaken the effect that pn ties, reduce local parallel resistance and form local electric leakage, cause battery failure, so solar cell preparation flow, technique, the design of parameter is directly connected to the stability of application, the parameter that affects solar cell performance all can affect PID effect (Pingel S in application process, Frank O, Winkler M, et al., Photovoltaic Specialists Conference (PVSC), 201035
thiEEE, 2010:002817-002822.).
Therefore, solar cell piece performance study and improvement are the essential places of eliminating PID effects in component application process.Easier regulation and control due to relative other techniques of antireflective coating, actively praises highly also one of widely used means so the silicon nitride anti-reflecting film of solar cell front surface becomes current a kind of quilt.There is researcher that monofilm is studied and improved: by carrying out substrate surface preliminary treatment (process gas plasma bombardment or non-process gas plasma bombardment), or control technological parameter and change antireflective coating sedimentary condition, improve antireflective coating refractive index, by suppressing the mode of the leakage current of solar cell or the conductivity of raising antireflection film layer, stop charged ion tired at antireflective coating surface layer, thereby reach the object of alleviating assembly PID effect.Yet the raising of antireflection film layer refractive index can cause solar cell conversion efficiency to reduce.There is researcher to adopt double layer antireflection coating (Pingel S, Frank O, Winkler M, et al., Photovoltaic Specialists Conference (PVSC), 201035
thiEEE.IEEE, 2010:002817-002822.) take into account light utilization and PID effect simultaneously, make solar cell can realize high conversion efficiency, there is again the performance of anti-PID effect.Have researcher to adopt the mode of double-layer reflection reducing coating, but result shows, with respect to double layer antireflection coating, when antireflective coating reaches more than three layers, the PID effect realizing is not further improved, and cannot eliminate the impact of PID effect yet yet.
Visible, double layer antireflection coating is the method that PID effect in component application is even eliminated in inhibition comparatively desirable in solar cell piece.There is various ways can realize the preparation of solar battery surface double layer antireflection coating: collosol and gel (R.B.Pettit, C.J.Brinker, C.S.Ashley, Solar Cells, Vol.15,1985:267-278; Shui-Yang Lien, Dong-Sing Wuu, Wen-Chang Yeh, et al., Solar Energy Materials & Solar Cells, Vol.90,2006:2710-2719), thermal oxidation (J.Zhao, A.Wang, P.Altermatt, M.A.Green, Applied Physics Letters, Vol.66,1995:3636-36338), vacuum evaporation (Jianhua Zhao, Aihua Wang, Martin A.Green, IEEE transactions on electron devices, Vol.41 (9), 1994:1592-1594) etc.Wherein spin coating collosol and gel directly easily causes the pollution of substrate surface at the two antireflective coatings of substrate surface preparation, also do not have good hydrogen passivation effect, and spin coating mode is unfavorable for Industry Promotion; High-temperature thermal oxidation mode can realize good surface passivation effect, but pyroprocess easily causes contaminating impurity, and length consuming time, is unfavorable for production cost control; And the equipment cost of vacuum evaporation higher, yield poorly, be also unfavorable for producing transition.On producing at present, generally adopt stable, easily control, plasma reinforced chemical vapour deposition simple to operate (PECVD) method, based on this technology mode, the rete of researcher's Effect of Anti PID effect, what have passes through control technological parameter at the antireflection film layer (S.Winderbaum of substrate surface deposition different refractivity, F.Yun, O.Reinhold, Journal of Vacuum Science and Technology A, Vol.15 (3), 1997:1020-1025), domestic Ye You producer adopts and prepares in this way antireflection film layer (the complete works of Solar Co., Ltd in Zhenjiang with anti-PID, the solar battery sheet of anti-PID effect and manufacture method thereof, 201310201143.4), because amorphous silicon layer has better conductivity, can avoid accumulation in assembly glued membrane, antireflection film layer (Tianhe Optical Energy Co., Ltd., Changzhou of " amorphous silicon/silicon nitride " and " silicon nitride/amorphous silicon/silicon nitride " structure has been prepared by some producers, the solar cell passivated reflection reducing membrane of the anti-PID effect of energy, 201310008588.0).Also the different precursor gas of importing having, deposit successively different rete formation passivated reflection reducings and penetrate rete, as import after nitrous oxide (being laughing gas), can be prepared into " silica/silicon nitride " double layer antireflection coating (CECEP Solar Energy Technology (Zhenjiang) Co., Ltd., crystal silicon solar electrode of a kind of anti-PID effect and preparation method thereof, 201310354011.5; New forms of energy Development Co., Ltd of Shanghai divine boat, a kind of anti-PID crystal silicon solar batteries, 201320484943.7); Also (the complete works of Solar Co., Ltd in Zhenjiang, has the crystalline silicon battery plate of anti-PID effect plated film, 201320292810.X) can be prepared into " nitrogenize silicon/oxidative silicon " anti-PID double layer antireflection coating; Can also be prepared into " nitrogen silica/silica " anti-PID double layer antireflection coating (Mai Ji solar energy Science and Technology Ltd. of DEC's group (Yixing), a kind of antireflective coating method with anti-PID effect of preparing).In addition, in the evolution of preparing in the research of photoinduction plating laser doping selective emitter solar battery, a kind of new two antireflection film layer preparation methods have also been formed: first adopt PECVD mode deposited monolayers silicon nitride film layer, and then adopt spin coating mode on silicon nitride film layer, to deposit silicon oxide film (ZhouChunlan, Li Tao, Song Yang, et al., Solar Energy, Vol.85, 2011:3057-3063), prepare the selective emitter solar battery of " silica/silicon nitride " double-layer reflection-decreasing membrane structure, its main purpose is to utilize the silicon oxide layer of spin coating to prevent from, in photoinduction electroplating process, transient occurs, to avoid the reduction (CAS Electrical Engineering Research Institute of solar cell conversion efficiency, number of patent application: 201110177712.7), comparatively speaking, the preparation method of this double layer antireflection coating is simple, cost is low, but spin coating mode is unfavorable for making the transition to industrialization industry.
In sum, two antireflective coatings are from solar cell itself, to avoid one of major way of even eliminating PID effects component application process.From membranous layer property, the antireflection film layer of high index of refraction can cause light absorption to increase, and suppresses the utilization of solar cell light, thereby reduces solar cell conversion efficiency; And the antireflection film layer of low-refraction is unfavorable for the impact of anti-PID effect.From preparation method, spin coating collosol and gel mode is unfavorable for industrialization realization, high-temperature oxydation mode production cost is too high and the cycle is long, and vacuum evaporation mode is not suitable for solar cell production yet.Thus, invention mode succinct, that be easy to industrialization is prepared the double layer antireflection coating both with anti-PID effect, can promote conversion efficiency again, becomes one of hot job of current solar cell development.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned double layer antireflection coating preparation method, propose a kind of post-processing approach of solar cell, realize the preparation of solar cell duplicature.Adopt a kind of post-processing approach that promotes sun conversion efficiency of the present invention to carry out reprocessing to current conventional solar cell, not only make solar cell can resist PID effect, and can effectively improve the conversion efficiency of solar cell, can make more than its conversion efficiency promotes 0.2% (abs.).
A kind of post-processing approach that promotes solar cell conversion efficiency of the present invention, so its feature is substrate take the solar cell preparing at present, carries out aftertreatment technology at the solar cell front surface preparing and completes.Specifically, to prepare solar cell according to current method, the solar cell preparing of take is substrate, at its front surface, carry out reprocessing, the solar cell front surface cvd silicon oxide precursor aqueous solution that the mode of i.e. employing spraying is preparing, after drying, annealing, form membranous layer of silicon oxide, thereby realize the preparation of solar cell front surface " silica/silicon nitride " double layer antireflection coating.
A kind of post-processing approach that promotes solar cell conversion efficiency of the present invention, its realization flow is divided into two joints on the whole: first segment is conventional solar cell preparation flow, technical process is making herbs into wool cleaning, High temperature diffusion, secondary cleaning, silicon nitride deposition, silk screen printing and sintering, test, and second section is reprocessing flow process: precursor aqueous solution deposition and annealing, test.
The processing step of post-processing approach of the present invention is specific as follows:
First segment conventional solar cell preparation flow, comprising:
(1) (1) making herbs into wool is cleaned and is dry
Substrate surface to be prepared is cleaned in corrosion.For monocrystalline silicon piece substrate, adopt aqueous slkali: potassium hydroxide or sodium hydroxide solution corrode; For multicrystalline silicon substrate, adopt the mixed solution of nitric acid and hydrofluoric acid to corrode cleaning.The main purpose one that corrosion is cleaned is that the damage layer of silicon chip surface is removed, to reduce recombination-rate surface, and the 2nd, at substrate surface, form the structure with good anti-reflective effect, to improve the incident light utilization of solar cell.After etching, adopt high purity deionized water fully to clean substrate, then that substrate surface is fully dry;
(2) High temperature diffusion
The substrate under 800～900 ℃ of conditions, step (1) being prepared spreads in diffusion furnace, makes silicon chip front surface thin layer because impurity compensation realizes transoid, forms crystal-silicon solar cell emitter;
(3) secondary cleaning
After High temperature diffusion, substrate perimeter has formed inversion layer, can cause the reduction of solar cell output parameter, therefore need to before battery preparation, the inversion layer of substrate perimeter be removed.The silicon chip having spread through step (2) is carried out to wet method and carve limit, remove on the one hand the inversion layer that substrate back and periphery form, on the other hand, the phosphorosilicate glass layer forming at substrate front surface in step (2) is cleaned up, and dry after fully cleaning;
(4) silicon nitride deposition
Under 300～500 ℃ of conditions, substrate prepared by step (3) adopts plasma reinforced chemical vapour deposition (PECVD) method at the silicon nitride film of its front surface deposition 80nm, the silicon nitride of deposition is the antireflective coating of front surface, is also the passivation film of front surface;
(5) silk screen printing
The substrate back electrode district depositing silver aluminium paste that the mode of employing silk screen printing makes in step (4) respectively, after oven dry, at the non-electrode zone deposition of aluminum of described substrate back slurry, after oven dry, then at described substrate front surface depositing silver slurry;
(6) sintering, test
The substrate for preparing electrode is placed in to Fast Sintering stove dries and sintering.The object of drying is mainly that organic solvent in substrate back and front surface slurry is fully volatilized, then sintering under 780～850 ℃ of temperature ranges, air or nitrogen atmosphere condition, make by alloy mode, to form good ohmic contact between electrode and substrate, at substrate back, realize aluminium doping simultaneously and form back surface field.
So far, complete the preparation of current conventional solar cell, can carry out output performance test to prepared solar cell;
Second section reprocessing flow process, comprising:
(7) precursor aqueous solution deposition
The conventional solar cell that completes described step (1)-(6) of take is substrate, promotes the aftertreatment technology of conversion efficiency.The conventional solar cell of having prepared of take is substrate, adopts spraying process at the front surface cvd silicon oxide precursor aqueous solution of solar cell, then under 100 ℃ of temperature, air atmosphere, dries.Described silica precursor aqueous solution is organic solution, and its solute is silicon-oxygen polymer, and solvent is alcohol or isopropyl alcohol, and concentration is 0.5～10.0%;
(8) annealing, test
By the conventional solar cell that has deposited precursor aqueous solution through step (7) 10～120s that anneals, form membranous layer of silicon oxide under 200～450 ℃ of temperature ranges, air or nitrogen atmosphere condition.So far complete a kind of reprocessing flow process that promotes solar cell conversion efficiency of the present invention, at conventional solar cell front surface, formed the solar cell double-layer reflection-decreasing membrane structure of anti-PID simultaneously.
Described step (1)-(6) are the preparation flows that current crystal-silicon solar cell is produced.The invention is characterized in that it take the conventional solar cell of having prepared is at present substrate, at solar cell front surface, adopt the mode of spraying to deposit the precursor aqueous solution of one deck silicon oxide film, i.e. described step (7); Be further characterized in that in described step (8) annealing process, precursor aqueous solution further decomposes, at solar cell front surface, form silicon oxide film, thereby make solar cell front surface there is " silica/silicon nitride " double-layer reflection-decreasing membrane structure, become the solar cell with anti-PID effect.Described membranous layer of silicon oxide has certain carbon content.
Utilize solar cell front surface prepared by the inventive method to there is double-layer reflection-decreasing membrane structure, can improve the incident light utilance of solar cell front surface, improve solar cell short circuit current, thereby promote the conversion efficiency of solar cell.The silicon oxide film that solar cell front surface forms can hide the gate electrode line of solar cell front surface to shelter well, avoids better solar cell front surface electrode grid line oxidized, strengthens the stability of solar cell performance.The membranous layer of silicon oxide that solar battery surface forms has certain carbon content, can improve film performance, reaches the effect of the anti-PID effect of solar cell.
The present invention has the following advantages:
(1) solar cell preparation flow is simple, and based on current solar cell, conventional preparation method realizes, compatible with current production procedure, easily realizes, and without production, operating personnel are additionally trained, saves personnel cost;
(2) solvent for use is for common are machine solvent, with low cost;
(3) rete depositional mode adopts spraying process, and technique is simple, easy to operate, repeatable strong, and industrialization is fast transition;
(4) silica forming at existing solar cell front surface can reduce solar cell front-side reflectivity, effectively improves solar cell short circuit current, improves solar cell conversion efficiency, more than making solar cell conversion efficiency lifting 0.2% (abs.);
(5) solar cell of preparing has anti-PID characteristic, has increased the stability of solar cell.
Accompanying drawing explanation
Fig. 1 the inventive method process flow diagram;
Fig. 2 conventional solar cell structural representation;
The solar battery structure schematic diagram that Fig. 3 the inventive method is prepared.
Embodiment
Below in conjunction with the drawings and the specific embodiments, further illustrate the present invention.
It is substrate that the solar cell that at present the general mode of production realizes is take in the present invention, adopt the mode of spraying at the front surface cvd silicon oxide precursor aqueous solution of solar cell, after drying under 100 ℃ of conditions, then the 10～120s that anneals within the scope of 200～450 ℃, under air or nitrogen atmosphere condition.
Figure 1 shows that the inventive method schematic flow sheet, the technological process of the inventive method divides two joints: first segment conventional solar cell preparation flow S-1 and second section reprocessing flow process S-2.
1, the processing step of first segment conventional solar cell preparation flow S-1 is with conventional solar cell preparation flow is identical at present.
As shown in Figure 1, first segment conventional solar cell preparation flow S-1 comprises:
Step S-101 making herbs into wool is cleaned and is dry: first silicon chip substrate N-010 is carried out to making herbs into wool cleaning and dry; Adopt potassium hydroxide or sodium hydroxide solution to corrode monocrystalline silicon piece, adopt acid solution to corrode multicrystalline silicon substrate, to remove the cutting damage layer of silicon chip surface, make substrate surface form the body structure surface N-011 with good anti-reflective effect simultaneously, the surface reflection and the surperficial charge carrier recombination rate that reduce solar cell, then adopt high purity deionized water fully to clean and dry silicon chip substrate N-010;
Step S-102 High temperature diffusion: the silicon chip substrate N-010 after step S-101 is dried carries out high temperature phosphorous diffusion under 800～900 ℃ of conditions, makes front surface carry out impurity compensation and transoid is prepared solar cell emitter N-012;
Step S-103 secondary wet process cleans: the silicon chip substrate N-010 after step S-102 High temperature diffusion is carried out to secondary cleaning, the inversion layer forming in high-temperature diffusion process to remove silicon chips periphery and the back side, the phosphorosilicate glass layer simultaneously silicon chip substrate N-010 front surface being formed cleans up, and dry.
Step S-104 silicon nitride deposition: after step S-103 completes, silicon chip substrate N-010 is carried out to silicon nitride deposition in 300～500 ℃ of temperature ranges, adopt plasma reinforced chemical vapour deposition (PECVD) method at the silicon nitride anti-reflecting film N-013 of the front surface deposition 80nm of silicon chip substrate N-010.The refractive index of silicon nitride anti-reflecting film layer N-013 is about 2.1, amorphous silicon nitride film layer is owing to containing a large amount of hydrogen, therefore this silicon nitride anti-reflecting film layer N-013 also has the effect of surface passivation for solar cell, further to reduce surface reflection and the recombination-rate surface of solar cell.
Step S-105 silk screen printing: the substrate back electrode district depositing silver aluminum slurry that the mode of employing screen printing prepares at step S-104, after oven dry, at the non-electrode district of described substrate back deposition of aluminum slurry, then dry, then at the front surface electrode district of described substrate depositing silver slurry;
Step S-106 sintering: the substrate that step S-105 is made is placed in Fast Sintering stove, approximately 780～850 ℃ of temperature ranges, carry out sintering, make the front surface of substrate and carry on the back between surface electrode and substrate to form good ohmic contact by alloy mode, become front surface electrode N-014 and the backplate N-015 of solar cell, impel back aluminium to adulterate in silicon simultaneously, form solar cell back surface field N-016.
So far, completed the preparation of conventional structure solar cell as shown in Figure 2, the front surface of this solar cell is silicon nitride individual layer antireflective coating.The conversion efficiency that this solar cell is realized can be tested and be obtained by I-V.
2, second section reprocessing flow process S-2, comprising:
Step S-201 precursor aqueous solution deposition, oven dry: the front surface cvd silicon oxide precursor aqueous solution of the conventional solar cell that employing spraying process makes at first segment: the silica precursor aqueous solution that is 0.5～10% by the concentration preparing adopts the mode of spraying to be deposited on solar cell front surface, under 100 ℃ of conditions, dries.
Step S-202 annealing, test: be that the solar cell of silicon oxide film precursor aqueous solution deposition is 200～450 ℃ of temperature ranges by having completed step S-201, 10～120s anneals under air or nitrogen atmosphere condition, under this annealing conditions, the silica precursor aqueous solution of solar cell front surface deposition decomposes, formation has the membranous layer of silicon oxide M-017 of certain carbon content, membranous layer of silicon oxide M-017 uniform fold is at whole solar cell front surface, obtain front surface and have the solar cell of " silica/silicon nitride " two antireflective coating structures, as shown in Figure 3, this solar cell has anti-PID effect.
With respect to conventional structure solar cell, the solar cell that adopts the inventive method to prepare has " silica/silicon nitride " two antireflective coating structures, wherein outermost layer silica has certain carbon content, can effectively reduce surface reflectivity, improve the short circuit current of solar cell, make more than the conversion efficiency of solar cell can improve 0.2% (abs.).
In following specific embodiment, making herbs into wool and secondary cleaning equipment are Rina equipment, and High temperature diffusion, PECVD and flash baking sintering furnace are Centrotherm equipment, and screen process press is ASYS equipment, and solar cell test is Burger equipment.In order specific implementation of the present invention to be realized to industrialization, make the transition, the post-depositional oven dry of the organic solution of silicon-oxygen polymer and annealing are carried out integrated, adopt Centrotherm flash baking sintering furnace dry and anneal, wherein bake out temperature is 100 ℃, and annealing peak temperature is 200～450 ℃, annealing time is 10～120s, and described silica precursor aqueous solution concentration is 0.5～10%.
Embodiment 1
1, by 156 * 156mm
2p type crystal silicon chip (polycrystalline) in Rina equipment, carry out acid corrosion making herbs into wool, fully standby after drying up with nitrogen after cleaning;
2, Centrotherm High temperature diffusion/oxidation furnace temperature is increased to 800 ℃, the cleaning silicon wafer that step 1 is prepared is placed on constant temperature region and carries out phosphorus diffusion, makes silicon chip front surface form n-type emitter;
3, silicon chip step 2 being made adopts Rina equipment to carry out secondary wet process etching, cleaning, is the inversion layer that removal substrate perimeter and the back side form in High temperature diffusion on the one hand, is that phosphorosilicate glass layer is cleaned up on the other hand;
4, after completing steps 3, silicon chip is directly placed in Centrotherm company tubular type " plasma reinforced chemical vapour deposition equipment ", under 300 ℃ of conditions, deposits silicon nitride anti-reflecting film, the about 80nm of institute's deposited silicon nitride antireflective coating thickness, refractive index approximately 2.1;
5, the silicon chip that step 4 made adopts ASYS screen process press at its back up silver aluminum slurry, republishes aluminum slurry after oven dry, then after drying at the front surface printed silver slurry of silicon chip;
6, the silicon chip that completes electrode printing through step 5 is placed in to Centrotherm flash baking sintering furnace is dried, sintering, the peak temperature of sintering is 780 ℃.So far complete the preparation of conventional solar cell.Adopt Burger to test its I-V characteristic, conventional solar cell short circuit current is 8.695A, and conversion efficiency is 17.52%;
7, preparation membranous layer of silicon oxide precursor aqueous solution: take alcohol as solvent, silicon-oxygen polymer is solute, the alcoholic solution of preparation silicon-oxygen polymer, solution concentration is 10.0%.The conventional solar cell that the step 6 of take makes is substrate, and the silicon-oxygen polymer alcoholic solution that the mode that adopts spraying is 10.0% by prepared concentration is deposited on the front surface of described conventional solar cell equably.
8, by the drying area Temperature Setting of Centrotherm flash baking sintering furnace, it is 100 ℃, the peak temperature of annealing under air atmosphere is 300 ℃, annealing time is 120s, by completing steps 7, is that solar cell that front surface has deposited silicon-oxygen polymer alcoholic solution is sent to Centrotherm flash baking sintering furnace and dries, anneals.The precursor aqueous solution of solar cell front surface deposition fully decomposes under annealing conditions, at front surface, forms membranous layer of silicon oxide, thereby realizes solar cell and have two antireflective coating structures of " silica/silicon nitride ".So far completed the preparation with two antireflection film layers and anti-PID solar cell.
9, the I-V characteristic that adopts the two antireflective coating solar cells of Burger test, its short circuit current is 8.814A, conversion efficiency is 17.79%.Thus, adopt a kind of post-processing approach that promotes solar cell conversion efficiency of the present invention to carry out after reprocessing conventional solar cell, realize solar cell short circuit current and improve 119mA, conversion efficiency improves 0.27%.
Embodiment 2
1, by substrate, be 156 * 156mm
2p type crystal silicon chip (polycrystalline) in Rina equipment, carry out acid corrosion making herbs into wool, fully standby after drying up with nitrogen after cleaning;
2, Centrotherm High temperature diffusion/oxidation furnace temperature is increased to 830 ℃, the cleaning silicon wafer that step 1 is prepared is placed on constant temperature region and carries out phosphorus diffusion, makes silicon chip front surface form n-type emitter;
3, silicon chip step 2 being made adopts Rina equipment to carry out secondary wet process etching, cleaning, removes on the one hand the inversion layer that substrate perimeter and the back side form in step 2 High temperature diffusion, on the other hand phosphorosilicate glass layer is cleaned up;
4, silicon chip step 3 being made is directly placed in Centrotherm company tubular type " plasma reinforced chemical vapour deposition equipment ", under 450 ℃ of conditions, deposit silicon nitride anti-reflecting film, the about 80nm of thickness of institute's deposited silicon nitride antireflective coating, refractive index approximately 2.1;
5, the silicon chip back side printed silver aluminum slurry that adopts ASYS screen process press to make in step 4, republishes aluminum slurry after oven dry, then after drying at silicon chip front surface printed silver slurry;
6, the silicon chip that has printed electrode is dried in Centrotherm flash baking sintering furnace, sintering, the peak temperature of sintering is 830 ℃.So far complete the preparation of conventional solar cell.The I-V characteristic that adopts Burger to test this conventional solar cell, this conventional solar cell short circuit current is 8.641A, conversion efficiency is 17.39%;
7, preparation membranous layer of silicon oxide forerunner is molten: take alcohol as solvent, silicon-oxygen polymer is solute, the alcoholic solution of preparation silicon-oxygen polymer, and solution concentration is 8%.The conventional solar cell of having prepared through step 6 of take is substrate, and the silicon-oxygen polymer alcoholic solution that the mode that adopts spraying is 8% by prepared concentration is deposited on the front surface of described conventional solar cell equably;
8, by the drying area Temperature Setting of Centrotherm flash baking sintering furnace, it is 100 ℃, the peak temperature of annealing under nitrogen atmosphere is 200 ℃, annealing time is 30s, by completing steps 7, is that solar cell that front surface has deposited silicon-oxygen polymer alcoholic solution is sent to Centrotherm flash baking sintering furnace and dries, anneals.The precursor aqueous solution of solar cell front surface deposition fully decomposes under annealing conditions, at front surface, form membranous layer of silicon oxide, thereby the two antireflective coating structures that realize solar cell and have " silica/silicon nitride ", have so far completed the preparation with two antireflection film layers and anti-PID solar cell.
9, the I-V characteristic that adopts the two antireflective coating solar cells of Burger test, its short circuit current is 8.742A, conversion efficiency is 17.62%.Thus, adopt a kind of post-processing approach that promotes solar cell conversion efficiency of the present invention to carry out after reprocessing conventional solar cell, realize solar cell short circuit current and improve 101mA, conversion efficiency improves 0.23%.
Embodiment 3:
1, by 156 * 156mm
2p type crystal silicon chip (polycrystalline) in Rina equipment, carry out acid corrosion making herbs into wool, fully standby after drying up with nitrogen after cleaning;
2, Centrotherm High temperature diffusion/oxidation furnace temperature is increased to 830 ℃, the cleaning silicon wafer that step 1 is prepared is placed on constant temperature region and carries out phosphorus diffusion, makes silicon chip front surface form n-type emitter;
3, silicon chip step 2 being completed adopts Rina equipment to carry out secondary wet process etching, cleaning, and the inversion layer of removing substrate perimeter and forming in High temperature diffusion overleaf on the one hand, cleans up phosphorosilicate glass layer on the other hand;
4, after completing steps 3, silicon chip is directly placed in Centrotherm company tubular type " plasma reinforced chemical vapour deposition equipment ", under 500 ℃ of conditions, deposits silicon nitride anti-reflecting film, the about 80nm of institute's deposited silicon nitride antireflective coating thickness, refractive index approximately 2.1;
5, the silicon chip back side printed silver aluminum slurry that adopts ASYS screen process press to make in step 4, prints aluminum slurry at this silicon chip back side after oven dry, after oven dry, at the front surface printed silver slurry of this silicon chip again;
6, the silicon chip that completes electrode printing through step 5 is placed in to Centrotherm flash baking sintering furnace is dried, sintering, the peak temperature of sintering is 850 ℃.So far complete the preparation of conventional solar cell.Adopt Burger to test its I-V characteristic, conventional solar cell short circuit current is 8.607A, and conversion efficiency is 17.34%;
7, preparation membranous layer of silicon oxide precursor aqueous solution: take isopropyl alcohol as solvent, silicon-oxygen polymer is solute, the aqueous isopropanol of preparation silicon-oxygen polymer, solution concentration is 10.0%.The conventional solar cell that the step 6 of take is prepared into is substrate, and the silicon-oxygen polymer aqueous isopropanol that the mode that adopts spraying is 10.0% by prepared concentration is deposited on the front surface of described conventional solar cell equably;
8, by the drying area Temperature Setting of Centrotherm flash baking sintering furnace, it is 100 ℃, the peak temperature of annealing under air atmosphere is 300 ℃, annealing time is 10s, by completing steps 7, is that solar cell that front surface has deposited silicon-oxygen polymer aqueous isopropanol is sent to Centrotherm flash baking sintering furnace and dries, anneals.The precursor aqueous solution of solar cell front surface deposition fully decomposes under annealing conditions, at front surface, forms membranous layer of silicon oxide, thereby realizes solar cell and have two antireflective coating structures of " silica/silicon nitride ".So far completed the preparation with two antireflection film layers and anti-PID solar cell.
9, the I-V characteristic that adopts the two antireflective coating solar cells of Burger test, its short circuit current is 8.762A, conversion efficiency is 17.64%.Thus, adopt post-processing approach of the present invention to carry out after reprocessing conventional solar cell, solar cell short circuit current improves 155mA, and conversion efficiency improves 0.30%.
Embodiment 4:
1, by substrate, be 156 * 156mm
2p type crystal silicon chip (polycrystalline) in Rina equipment, carry out acid corrosion making herbs into wool, fully standby after drying up with nitrogen after cleaning;
2, Centrotherm High temperature diffusion/oxidation furnace temperature is increased to 900 ℃, the cleaning silicon wafer that step 1 is prepared is placed on constant temperature region and carries out phosphorus diffusion, makes silicon chip front surface form n-type emitter;
3, silicon chip step 2 being made adopts Rina equipment to carry out secondary wet process etching, cleaning, removes on the one hand the inversion layer that substrate perimeter and the back side form in step 2, on the other hand phosphorosilicate glass layer is cleaned up;
4, silicon chip step 3 being made is directly placed in Centrotherm company tubular type " plasma reinforced chemical vapour deposition equipment ", under 450 ℃ of conditions, deposit silicon nitride anti-reflecting film, the about 80nm of thickness of institute's deposited silicon nitride antireflective coating, refractive index approximately 2.1;
5, the silicon chip back side printed silver aluminum slurry that adopts ASYS screen process press to make in step 4, prints aluminum slurry at this silicon chip back side after oven dry, after oven dry, at the front surface printed silver slurry of this silicon chip again;
6, the silicon chip that has printed electrode is dried in Centrotherm flash baking sintering furnace, sintering, the peak temperature of sintering is 830 ℃.So far complete the preparation of conventional solar cell.Adopt Burger to test its I-V characteristic, conventional solar cell short circuit current is 8.593A, and conversion efficiency is 17.33%;
7, preparation membranous layer of silicon oxide forerunner is molten: take alcohol as solvent, silicon-oxygen polymer is solute, the alcoholic solution of preparation silicon-oxygen polymer, and solution concentration is 0.5%.Conventional solar cell prepared by the step 6 of take is substrate, and the silicon-oxygen polymer alcoholic solution that the mode that adopts spraying is 0.5% by prepared concentration is deposited on the front surface of described conventional solar cell equably;
8, by the drying area Temperature Setting of Centrotherm flash baking sintering furnace, it is 100 ℃, the peak temperature of annealing under nitrogen atmosphere is 450 ℃, annealing time is 30s, by completing steps 7, is that solar cell that front surface has deposited silicon-oxygen polymer alcoholic solution is sent to Centrotherm flash baking sintering furnace and dries, anneals.The precursor aqueous solution of solar cell front surface deposition fully decomposes under annealing conditions, at front surface, form membranous layer of silicon oxide, make solar cell there are two antireflective coating structures of " silica/silicon nitride ", so far completed the preparation with two antireflection film layers and anti-PID solar cell.
The I-V characteristic that adopts the two antireflective coating solar cells of Burger test, its short circuit current is 8.707A, conversion efficiency is 17.55%.Thus, adopt post-processing approach of the present invention to carry out after reprocessing conventional solar cell, solar cell short circuit current improves 114mA, and conversion efficiency improves 0.22%.
Claims (4)
1. a post-processing approach that promotes solar cell conversion efficiency, is characterized in that, described post-processing approach comprises the following steps:
First segment, conventional solar cell preparation flow:
(1) making herbs into wool is cleaned and is dry: substrate surface to be prepared is cleaned in corrosion, and fully dry;
(2) High temperature diffusion: under hot conditions, the substrate preparing in step (1) is carried out to phosphorus diffusion, form n-type emitter;
(3) secondary cleaning: the substrate having spread in step (2) is carried out to wet method and carve limit, cleaning dry;
(4) silicon nitride deposition: the substrate that step (3) is made adopts plasma reinforced chemical vapour deposition method at substrate front surface deposited silicon nitride antireflective coating;
(5) silk screen printing: the substrate front surface depositing silver slurry that the mode of employing silk screen printing makes in step (4) respectively, at described substrate, carry on the back surperficial electrode district depositing silver aluminium paste, at the non-electrode zone deposition of aluminum of described substrate back slurry;
(6) sintering, test: the substrate of completing steps (5) silk screen printing is carried out to sintering, form good electrode ohmic contact, complete the preparation of conventional solar cell;
Second section, reprocessing flow process:
(7) precursor aqueous solution deposition, oven dry: the conventional solar cell that the step (6) of take prepares is substrate, adopt spraying process to dry at its front surface cvd silicon oxide precursor aqueous solution and under 100 ℃ of conditions, makes organic solvent volatilization in precursor aqueous solution;
(8) annealing, test: the substrate that step (7) the is made 10～120s that anneals under 200～450 ℃ of temperature ranges, air or nitrogen atmospheres, makes the silica precursor aqueous solution of deposition fully volatilize, be decomposed to form membranous layer of silicon oxide.
2. the post-processing approach of lifting solar cell conversion efficiency according to claim 1, it is characterized in that, solar cell front surface through reprocessing is " silica/silicon nitride " two antireflective coatings, described silica is to take conventional solar cell as substrate, at front surface, adopt spraying process cvd silicon oxide precursor aqueous solution, after oven dry, in annealing process, be decomposed to form, described silicon oxide film rete contains carbon.
3. the post-processing approach of lifting solar cell conversion efficiency according to claim 1, it is characterized in that described precursor aqueous solution is organic solution, wherein solute is silicon-oxygen polymer, and solvent is alcohol or isopropyl alcohol, and the concentration of described precursor aqueous solution is 0.5～10%.
4. the post-processing approach of lifting solar cell conversion efficiency according to claim 1, is characterized in that oven dry in described step (7) and the annealing of step (8) carries out in same chain type production equipment.
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