CN103681942B - The preparation method of crystalline silicon SE solar cell piece and crystalline silicon SE solar cell piece - Google Patents
The preparation method of crystalline silicon SE solar cell piece and crystalline silicon SE solar cell piece Download PDFInfo
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- CN103681942B CN103681942B CN201210317479.2A CN201210317479A CN103681942B CN 103681942 B CN103681942 B CN 103681942B CN 201210317479 A CN201210317479 A CN 201210317479A CN 103681942 B CN103681942 B CN 103681942B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910021419 crystalline silicon Inorganic materials 0.000 title abstract description 34
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 70
- 239000010703 silicon Substances 0.000 claims abstract description 70
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000137 annealing Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 23
- 239000006117 anti-reflective coating Substances 0.000 claims abstract description 22
- 238000007747 plating Methods 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 238000009792 diffusion process Methods 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 9
- 235000008216 herbs Nutrition 0.000 claims abstract description 8
- 210000002268 wool Anatomy 0.000 claims abstract description 8
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 35
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 35
- 229910052709 silver Inorganic materials 0.000 claims description 33
- 239000004332 silver Substances 0.000 claims description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 230000009972 noncorrosive effect Effects 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 238000009713 electroplating Methods 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000005477 sputtering target Methods 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000005611 electricity Effects 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 42
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 14
- 229920005591 polysilicon Polymers 0.000 description 14
- 239000002002 slurry Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241001226615 Asphodelus albus Species 0.000 description 1
- 101100373011 Drosophila melanogaster wapl gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010017 direct printing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 210000004483 pasc Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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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
- H01L31/18—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 System
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
-
- 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
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022433—Particular geometry of the grid contacts
-
- 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
-
- 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
Abstract
The invention provides a kind of preparation method of crystalline silicon SE solar cell piece, comprise the following steps: S1, making herbs into wool, diffusion, the process of dephosphorization silex glass are carried out to silicon chip surface, then at front side of silicon wafer plating silicon nitride anti-reflecting film; S2, at antireflective coating surface coverage layer of metal mask, then adopt magnetron sputtering method deposited oxide bismuth on antireflective coating; S3, at silicon chip back side printed back conductive silver slurry and back field aluminum paste material, entirety enter continuous tunnel furnace sintering, sintered after annealing; S4, carry out photoinduction plating at front side of silicon wafer, obtain described crystalline silicon SE solar cell piece.Present invention also offers the crystalline silicon SE solar cell piece adopting this preparation method to prepare.Preparation method's technique provided by the invention is simple, with low cost, can realize large-scale production, the crystalline silicon SE solar cell piece prepared, and its surface electrode grid line is fine and closely woven, masked area is little, and the series resistance of battery is little, and fill factor, curve factor increases, electricity conversion is high, with low cost.
Description
Technical field
The invention belongs to technical field of solar batteries, the preparation method particularly relating to a kind of crystalline silicon SE solar cell piece and the crystalline silicon SE solar cell piece prepared by this preparation method.
Background technology
Solar energy is as a kind of green energy resource, inexhaustible with it, pollution-free, be not more and more subject to people's attention by the advantage such as resource advantage restriction.Existing crystal silicon solar energy battery is generally adopt Screen-printed conductive slurry on silicon substrate, carries out drying and fire preparing electrode and back surface field.The phototropic face of crystal-silicon solar cell adopts silk screen printing front side silver paste after coated with antireflection film, then front silver electrode is directly obtained after crossing continuous tunnel furnace sintering, the receptance of the making energy appreciable impact light of front electrode, thus affect short circuit current and the photoelectric conversion efficiency of battery; The Structure and Properties research of electrode is emphasis and the focus of the research of current crystal silicon cell.
A technique of the commonplace employing of current efficient solar battery is selective emitter (being called for short SE) battery structure, the method refers to be formed under phototropic face metal electrode heavily spread, and shallow diffusion is formed in other regions, heavily spreading of such local, can make electrode and silicon form good ohmic contact, increase the fill factor, curve factor of battery, and sub-compound can be reduced less at shallow diffusion zone, improve the collection rate of photo-generated carrier.Use on producing realize selective emitter battery preferably technology be direct printing mask layer method; this method feature is for once heavily to spread; namely the heavy diffusion layer under mask protection silver electrode is utilized; corrosion forms the shallow diffusion of emitter region; compared with making with common batteries; extra increase cost is few, and the difficulty of this technique is to spread all even follow-up printing alignment.
Patent CN102270703A discloses a kind of preparation method of crystal silicon solar cell with selective emitter, the method adopts antimony target to carry out magnetron sputtering antimony diffusion layer, then in anemostat, the diffusion of phosphorus source is carried out, plate silicon nitride film, printing, sintering again, obtain crystal silicon solar cell with selective emitter, although this technique cost is low, can suitability for industrialized production, but still exist front side silver paste material and antimony diffusion layer to direct problem, and may there is bad reaction in silver layer and antimony layers, thus affect the adhesive force of electrode wires and silicon base under the atmosphere of humidity.
Summary of the invention
The invention solves in prior art and prepare the comparatively difficult technical problem of crystalline silicon SE solar cell piece existence diffusion all even printing alignment, and provide a kind of technique simple, with low cost, can large-scale production be realized, simultaneously crystalline silicon SE solar cell piece that can improve electricity conversion and preparation method thereof.
Particularly, the invention provides a kind of preparation method of crystalline silicon SE solar cell piece, comprise the following steps:
S1, making herbs into wool, diffusion, the process of dephosphorization silex glass are carried out to silicon chip surface, then at front side of silicon wafer plating silicon nitride anti-reflecting film;
S2, at antireflective coating surface coverage layer of metal mask, the hollow part shape of described metal mask is identical with the shape of phototropic face gate electrode line; Then adopt magnetron sputtering method deposited oxide bismuth on antireflective coating, sputtered rear removal metal mask, obtained bismuth oxide grid line layer;
S3, at silicon chip back side printed back conductive silver slurry, printing back field aluminum paste material after drying, after oven dry, silicon chip entirety is entered continuous tunnel furnace sintering, after having sintered, carry out annealing in process, the back side must be arrived and be formed with the silicon chip that back silver electrode and aluminium back surface field, front are formed with Seed Layer grid line;
S4, carry out photoinduction plating on the Seed Layer grid line surface of front side of silicon wafer, form phototropic face gate electrode line, obtain described crystalline silicon SE solar cell piece.
Present invention also offers a kind of crystalline silicon SE solar cell piece, described crystalline silicon SE solar cell piece is prepared by preparation method provided by the invention.
Crystalline silicon SE solar cell piece preparation method provided by the invention, by at antireflective coating surface magnetic control sputtering bismuth oxide layer, during sintering, itself and antireflective coating react and penetrate antireflective coating, thus contact with silicon chip substrate and react, elemental metals bismuth is formed at silicon chip surface, during annealing in process, bismuth metal fully diffuses in silicon chip substrate and forms N-type high-concentration dopant, namely under realizing electrode wires, N+ selectivity spreads, selective emitter region is formed at the phototropic face of cell piece, after photoinduction plating, crystalline silicon SE solar cell piece provided by the invention can be obtained, its surface electrode grid line is fine and closely woven, masked area is little, the series resistance of battery is little, fill factor, curve factor increases, electricity conversion is high, simultaneously because phototropic face electrode need not print electrode slurry, can effectively reduce costs.
Accompanying drawing explanation
Fig. 1 is the structural representation of crystalline silicon SE solar cell piece provided by the invention.
Wherein, 1---silver coating, 2---non-corrosive metal (NCM) layer, 3---Seed Layer grid line, 4---antireflective coating, 5---silicon chip, 6---back silver electrode, 7---aluminium back surface field.
Embodiment
The invention provides a kind of preparation method of crystalline silicon SE solar cell piece, comprise the following steps:
S1, making herbs into wool, diffusion, the process of dephosphorization silex glass are carried out to silicon chip 5 surface, then at silicon chip 5 front plating silicon nitride anti-reflecting film 4;
S2, at antireflective coating 4 surface coverage layer of metal mask, the hollow part shape of described metal mask is identical with the shape of phototropic face gate electrode line; Then adopt magnetron sputtering method deposited oxide bismuth on antireflective coating 4, sputtered rear removal metal mask, obtained bismuth oxide grid line layer;
S3, at silicon chip 5 back up back silver electrocondution slurry, printing back field aluminum paste material after drying, after oven dry, silicon chip entirety is entered continuous tunnel furnace sintering, after having sintered, carry out annealing in process, the back side must be arrived and be formed with the silicon chip 5 that back silver electrode 6 and aluminium back surface field 7, front are formed with Seed Layer grid line 3;
S4, carry out photoinduction plating on the Seed Layer grid line surface in silicon chip 5 front, form phototropic face gate electrode line, obtain described crystalline silicon SE solar cell piece.
The present inventor thinks, the principle forming selective emitter region in the present invention is: antireflective coating 4 is silicon nitride film, the bond energy of wherein nitrogen-silicon key is less, under high-temperature process (i.e. follow-up sintering and annealing in process), bismuth oxide in the bismuth oxide grid line layer of magnetron sputtering can with the silicon nitride reaction in antireflective coating 4, and produce silica and elemental metals bismuth, bismuth oxide grid line layer is so just made to penetrate antireflective coating 4, the bismuth oxide being perforated through antireflective coating 4 continues to react with silicon chip 5, generate more elemental metals bismuth and be trapped in the Seed Layer grid line 3 silicon chip 5 being formed phototropic face electrode, simultaneously, when annealing in process, bismuth metal fully diffuses in silicon chip 5 substrate and forms N-type high-concentration dopant, namely under realizing electrode wires, N+ selectivity spreads, thus form selective emitter region at the phototropic face of cell piece, after photoinduction plating, crystalline silicon SE solar cell piece provided by the invention can be obtained.
As previously mentioned, contact in silicon chip 5 after bismuth oxide grid line layer penetrates antireflective coating 4 and continue reaction, finally forming described Seed Layer grid line 3.Therefore, the active ingredient in this Seed Layer grid line 3 mainly comprises: the elemental metals bismuth generated after reaction and silica, and unreacted bismuth oxide completely.
In the present invention, first making herbs into wool, diffusion, the process of dephosphorization silex glass are carried out to silicon chip surface, then at front side of silicon wafer plating silicon nitride anti-reflecting film.The various monocrystalline silicon piece that described silicon chip can adopt those skilled in the art to commonly use or polysilicon chip, the present invention is not particularly limited.Such as, described silicon chip can adopt the polysilicon of 156 × 156mm to run.The step of described making herbs into wool, diffusion, dephosphorization silex glass and coated with antireflection film is identical with the manufacture craft of traditional solar cell, and the present invention is not particularly limited, and repeats no more herein.
According to method of the present invention, then magnetron sputtering process is carried out to silicon chip surface, specifically comprise: at antireflective coating surface coverage layer of metal mask, then adopt magnetron sputtering apparatus, with bismuth oxide target for sputtering target, at antireflection film layer surface deposition one deck bismuth oxide layer.In the present invention, the shape of the hollow part shape phototropic face gate electrode line of described metal mask is identical, and the shape of the bismuth oxide layer therefore deposited is then identical with the shape of phototropic face gate electrode line.
In the present invention, described metal mask can adopt various masks conventional in prior art, such as, can adopt metal molybdenum mask, but be not limited to this.
Described magnetron sputtering adopts magnetron sputtering apparatus to carry out, such as, can adopt linear pattern magnetron sputter, but be not limited to this.In the present invention, the condition of described magnetron sputtering preferably include for: sputtering target is bismuth oxide target, and sputtering pressure is 0.5 ~ 0.9Pa, sputters in argon atmosphere and carries out, and argon flow amount is 10 ~ 30sccm, and during sputtering, silicon temperature is 200 ~ 300 DEG C.
Sputtering time suitably can be selected according to the thickness of the required bismuth oxide deposited on silicon chip.The present inventor finds, be used at later transformation being Seed Layer grid line due to bismuth oxide grid line layer, therefore its deposit thickness needs Cautious control; Particularly, when bismuth oxide thickness is too little, the bismuth oxide obtained is not enough to form Seed Layer presoma, and the electric conductivity of the bismuth metal formed with pasc reaction is inadequate, unfavorable to subsequent optical induction electroplating technology, and bad to the doping effect of silicon chip; And thickness too large time, to cause in Seed Layer grid line bismuth oxide content too large, be unfavorable for the reduction of electrode volume resistance, because the resistivity of Seed Layer is much higher relative to follow-up plated metal silver.Therefore, in the present invention, the thickness of bismuth oxide grid line layer is preferably 1-5 μm.
As the common practise of those skilled in the art, the gate electrode line on solar cell piece surface, its fine and closely woven degree is more high better, thus effectively can reduce masked area.In the present invention, described phototropic face electrode is formed in Seed Layer grid line surface light induction plating by follow-up, and therefore the impact of the live width of Seed Layer grid line is most important, and therefore, in the present invention, when magnetron sputtering forms bismuth oxide layer, its live width is the smaller the better.Under preferable case, the grid line live width of bismuth oxide grid line layer is 2-15 μm.
According to method of the present invention, after the phototropic face of silicon chip forms bismuth oxide grid line, then the back side of silicon chip is processed, namely first print conductive silver slurry at silicon chip back side, printing back field aluminum paste material after drying, and dry; Then silicon chip entirety is sent into continuous tunnel furnace to sinter, after having sintered, carry out annealing in process.Sintering and annealing process in, formed except selection emitter region (namely front side of silicon wafer forms Seed Layer grid line) process except the foregoing bismuth oxide of generation penetrates antireflective coating, also comprise the process that silver electrode paste forms back silver electrode, back field aluminum paste material forms aluminium back surface field of silicon chip back side.
Described back silver electrocondution slurry, back field aluminum paste material are the various conventional slurry that those skilled in the art commonly use, and the present invention is not particularly limited, and repeats no more herein.
The condition of described sintering is with to sinter the sintering condition forming electrode in the slurry that prints electrode in prior art identical, and the present invention is not particularly limited.Such as, the condition of described sintering is: the total time crossing continuous tunnel furnace is 2-3min, and the peak temperature of sintering is 910 ± 10 DEG C, and the sintering time under peak temperature is 1 ~ 2s.
Described annealing in process is held for some time at an annealing temperature.In the present invention, the annealing temperature that annealing in process is and time need strict control; Annealing temperature is too high, the time is oversize, and secondary diffusion occurs the PN that previous diffuser can be caused to obtain, and PN junction gos deep in silicon, causes cell photoelectric transformation efficiency to reduce; Otherwise annealing temperature is too low, the time is too short, the bismuth metal that bismuth oxide reduction can be caused to be formed is inadequate to the N+ type doping content of silicon chip, effectively can not form selective emitter.Particularly, in the present invention, annealing temperature is 500-560 DEG C, and the annealing in process time is 2-10min.
According to method of the present invention, then photoinduction plating is carried out to the Seed Layer grid line surface of front side of silicon wafer, form phototropic face gate electrode line, described crystalline silicon SE solar cell piece can be obtained.
In the present invention, described photoinduction electroplating technology (LIP), for conventionally known to one of skill in the art, is included in Seed Layer grid line surface electrical silver-plated, forms phototropic face silver electrode.
Because between the silver of phototropic face silver electrode and bismuth metal, potential difference is less, very easily generating electrodes corrosion phenomenon in wet environment; Therefore, as a kind of preferred implementation of the present invention, in the present invention, described photoinduction plating comprises first at Seed Layer grid line electroplating surface non-corrosive metal (NCM) layer, then continues plated metal silver layer on non-corrosive metal (NCM) layer surface.In the present invention, the metal that described non-corrosive metal (NCM) layer adopts can be selected from nickel, palladium, gold, platinum any one.When described non-corrosive metal (NCM) layer selects metallic nickel, although its low price, it compares silver-colored and bismuth pole potential difference is less, and in wet environment, still easily mode is corroded; If select gold or platinum, its selling at exorbitant prices, unfavorable in cost; Therefore, the optimal selection of described non-corrosive metal (NCM) layer is metal palladium layers, and it has anticorrosion and cheap double dominant concurrently.
The thickness of non-corrosive metal (NCM) layer is unsuitable too small, otherwise its antiseptic effect is too faint; Also unsuitable excessive, otherwise significantly can increase cost.Under preferable case, the thickness of described non-corrosive metal (NCM) layer is 1-5 μm.
The thickness of described metallic silver layer makes phototropic face gate electrode line thickness in the present invention meet solar cell piece phototropic face thickness of electrode in prior art to require.Under preferable case, the thickness of described metallic silver layer is 5-15 μm.
The step of described photoinduction plating is conventionally known to one of skill in the art, such as the step of described photoinduction electrosilvering comprises: silicon chip entirety surface being formed with non-corrosive metal (NCM) layer puts into electrolysis tank as the negative electrode of electrolysis, using fine silver rod as the anode of electrolysis, using water-soluble silver salt solution as electrolyte, non-corrosive metal (NCM) layer plated surface last layer metallic silver layer.Under preferable case, electrolyte temperature is 35-40 DEG C, and electroplating time suitably can be selected according to the desired thickness of silver coating, is preferably 5-20min.
Electroplate rear drying, namely obtain crystalline silicon SE solar cell piece provided by the invention.Therefore, present invention also offers a kind of crystalline silicon SE solar cell piece, described crystalline silicon SE solar cell piece is prepared by preparation method provided by the invention.
Particularly, described crystalline silicon SE solar cell piece has structure shown in Fig. 1, comprises the silicon chip 5 as substrate, and the phototropic face of silicon chip 5 has antireflective coating 4 and phototropic face gate electrode line, and the back side of silicon chip 5 has back silver electrode 6 and aluminium back surface field 7; Wherein, phototropic face gate electrode line is three-decker, comprise Seed Layer grid line 3, non-corrosive metal (NCM) layer 2 and silver coating from bottom to up successively, Seed Layer grid line 3 is obtained through the process of sintering after annealing by bismuth oxide layer, make this Seed Layer grid line 3 penetrate antireflective coating 4 to contact with silicon chip 5, form selective emitter region.
Crystalline silicon SE solar cell piece provided by the invention, its surface electrode grid line is fine and closely woven, and masked area is little, and the series resistance of battery is little, and fill factor, curve factor increases, and electricity conversion is high; Simultaneously because phototropic face electrode need not print electrode slurry, can effectively reduce costs.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
(1) to the P type polysilicon of 156 × 156mm carry out making herbs into wool, cleaning and dry, organophosphor diffusion, etching, dephosphorization silex glass, then front side of silicon wafer plating silicon nitride anti-reflecting film, obtain P type polysilicon chip.
(2) P type polysilicon chip is placed on the slide holder of linear pattern magnetron sputter, its front covers upper metal molybdenum mask plate, fixing P type polysilicon chip and metal molybdenum mask plate, then its entirety is put into sputtering chamber, sputter to be fixed on bismuth oxide (purity > 99.9wt%) in chamber in advance for target, close sputtering chamber door, chamber is vacuumized ailing as argon gas, sputtering pressure is 0.7Pa, argon flow amount is 15sccm, silicon temperature is 240 DEG C, sputtering time is 20s, metal molybdenum mask plate is removed after having sputtered, realize the bismuth oxide film deposition of the grid region of P type polysilicon chip, the thickness depositing the bismuth oxide grid line layer obtained is 2.0 ± 0.2 μm, live width is 8.0 ± 0.5 μm.
(3) back side of P type polysilicon chip is adopted 200 order silk screen printing back silver electrocondution slurry (Du Pont PV505, three eight sections, line systems), adopt 280 order silk screen printing back field aluminum paste material (large standing grain 108C) again after 150 DEG C of oven dry, 150 DEG C of oven dry, drying time is 5 minutes.
(4) then sinter in the silicon chip entirety feeding continuous tunnel furnace of step (3), the total time crossing continuous tunnel furnace is 2-3min, and the peak temperature of sintering is 910 ± 10 DEG C, and the sintering time under peak temperature is 1 ~ 2s.After having sintered, silicon chip entirety is put into 520 DEG C of annealing furnaces, insulation 8min, the back side must be arrived and be formed with the polysilicon chip that back silver electrode and aluminium back surface field, front are formed with Seed Layer grid line.
(5) adopt photoinduction electroplating technology in the plating of the enterprising row metal palladium layers of the Seed Layer grid line of polysilicon chip, the thickness of palladium coating is 3.0 ± 0.2 μm, then again at metal palladium layers glazing induction plated metal silver, the thickness of silvering is 12 ± 0.5 μm, and silver-plated amount is 130mg; Go out groove after plating, with hot blast drying, namely obtain the crystalline silicon SE solar cell piece of the present embodiment, be designated as S1.
Embodiment 2
Adopt the step identical with embodiment 1 to prepare the crystalline silicon SE solar cell piece of the present embodiment, difference is:
In step (2), P type polysilicon chip is placed on the slide holder of linear pattern magnetron sputter, its front covers upper metal molybdenum mask plate, fix this P type polysilicon chip and metal molybdenum mask plate, then its entirety is put into sputtering chamber, sputter to be fixed on chamber internal oxidition bismuth (purity > 99.9wt%) in advance for target, close sputtering chamber door, chamber is vacuumized and passes into argon gas, sputtering pressure is 0.6Pa, argon flow amount is 18sccm, silicon temperature is 240 DEG C, sputtering time is 30s, metal molybdenum mask plate is removed after having sputtered, realize the bismuth oxide film deposition of the grid region of P type polysilicon chip, the thickness depositing the bismuth oxide grid line layer obtained is 5.0 ± 0.2 μm, live width is 15 ± 0.5 μm,
In step (4), annealing temperature is 550 DEG C, and the temperature retention time of annealing in process is 5min;
In step (5), the thickness adopting palladium coating is 1.0 ± 0.2 μm, and the thickness of silvering is 11 ± 0.5 μm, and silver-plated amount is 130mg.
By above-mentioned steps, obtain the crystalline silicon SE solar cell piece S2 of the present embodiment.
Comparative example 1
Making herbs into wool is carried out to the P type polysilicon of 156 × 156mm, clean and dry, organophosphor spreads, organic wax mask coating, surrounding etches, dephosphorization silex glass, plating silicon nitride anti-reflecting film, silk screen printing back silver electrocondution slurry (Du Pont PV505, three eight sections, line systems), back field aluminum paste material (large standing grain 108C) and front conductive silver slurry (Du Pont 17A, after sintering, width is 45 μm, line is high is 10 μm), then overall continuous tunnel furnace of crossing sinters, then on front electrode grid line, photoinduction electrosilvering is carried out, electroplating the silver layer height obtained is 4.0 ± 0.5 μm, silver-plated amount is 50mg, go out groove after plating, with hot blast drying, obtain the crystalline silicon SE solar cell piece of this comparative example of tool, be designated as DS1.
Performance test
1, surface appearance: adopt 3 ~ 5 times of magnifying glasses to observe the surface appearance of the phototropic face electrode of solar battery sheet sample S1-S2 and DS1 of above-mentioned preparation; If smooth surface, without plot point, without hole, be designated as OK, otherwise be designated as NG.
2, weld strength: select victory footpath between fields, Shanghai 2 × 0.2mm tin lead welding band, soaks post-drying with Henkel X32-10I type scaling powder, then carries out manual welding at 330 DEG C to the phototropic face electrode main grid line of solar cell piece sample S1-S2 and DS1; After each solar cell piece sample cools naturally, the electrode using mountain degree SH-100 puller system to connect along 45 ° of direction butt welding carries out tensile test, and unit is N.
3, fill factor, curve factor and electricity conversion: adopt single flash operation simulation test instrument to test solar cell piece sample S1-S2 and DS1.Test condition is standard test condition (STC): light intensity: 1000W/m
2; Spectrum: AM1.5; Temperature: 25 DEG C.Repeat 200 times, the mean value of record electricity conversion.
Test result is as following table 1.
Table 1
。
As can be seen from table 1, the test result of S1-S2 and DS1 relatively, the crystalline silicon SE solar cell piece adopting preparation method provided by the invention to obtain, its phototropic face gate electrode line is fine and closely woven, shading-area is little, high with the weld strength of photovoltaic welding belt, battery fill factor, curve factor is large, and therefore its average light photoelectric transformation efficiency is significantly improved.In addition, in preparation method provided by the invention, the phototropic face electrode of solar cell piece does not need printing front side silver paste material, therefore effectively can reduce the cost of manufacture of phototropic face electrode, increase the competitiveness of the generating of crystalline silicon SE solar cell piece and conventional electric power generation.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for crystal silicon solar cell with selective emitter sheet, is characterized in that, comprises the following steps:
S1, making herbs into wool, diffusion, the process of dephosphorization silex glass are carried out to silicon chip surface, then at front side of silicon wafer plating silicon nitride anti-reflecting film;
S2, at antireflective coating surface coverage layer of metal mask, the hollow part shape of described metal mask is identical with the shape of phototropic face gate electrode line; Then adopt magnetron sputtering method deposited oxide bismuth on antireflective coating, sputtered rear removal metal mask, obtained bismuth oxide grid line layer; Contact with silicon chip after described bismuth oxide grid line layer penetrates antireflective coating and react, forming Seed Layer grid line;
S3, at silicon chip back side printed back conductive silver slurry, printing back field aluminum paste material after drying, after oven dry, silicon chip entirety is entered continuous tunnel furnace sintering, after having sintered, carry out annealing in process, the back side must be arrived and be formed with the silicon chip that back silver electrode and aluminium back surface field, front are formed with Seed Layer grid line;
S4, carry out photoinduction plating on the Seed Layer grid line surface of front side of silicon wafer, form phototropic face gate electrode line, obtain described crystal silicon solar cell with selective emitter sheet.
2. preparation method according to claim 1, is characterized in that, in step S2, the metal that described metal mask adopts is molybdenum.
3. preparation method according to claim 1, is characterized in that, in step S2, the condition of magnetron sputtering comprises: sputtering target is bismuth oxide target, and sputtering pressure is 0.5-0.9Pa, sputters in argon atmosphere and carries out, and argon flow amount is 10-30sccm, during sputtering, silicon temperature is 200-300 DEG C.
4. the preparation method according to any one of claim 1-3, is characterized in that, in step S2, the grid line live width of bismuth oxide grid line layer is 2-15 μm, and the thickness of bismuth oxide grid line layer is 1-5 μm.
5. preparation method according to claim 1, is characterized in that, in step S3, sintering condition comprises: the total time crossing continuous tunnel furnace is 2-3min, and the peak temperature of sintering is 910 ± 10 DEG C, and the sintering time under peak temperature is 1-2s.
6. preparation method according to claim 1 or 5, it is characterized in that, in step S3, annealing temperature is 500-560 DEG C, and the annealing in process time is 2-10min.
7. preparation method according to claim 1, is characterized in that, in step S4, described photoinduction plating comprises first at Seed Layer grid line electroplating surface non-corrosive metal (NCM) layer, then continues plated metal silver layer on non-corrosive metal (NCM) layer surface.
8. preparation method according to claim 7, is characterized in that, in step S4, the metal that described non-corrosive metal (NCM) layer adopts be selected from nickel, palladium, gold, platinum any one; The thickness of non-corrosive metal (NCM) layer is 1-5 μm; The thickness of metallic silver layer is 5-15 μm.
9. the preparation method according to claim 7 or 8, is characterized in that, the electrolyte temperature adopted during photoinduction plating is 35-40 DEG C, and electroplating time is 5-20min.
10. a crystal silicon solar cell with selective emitter sheet, is characterized in that, described crystal silicon solar cell with selective emitter sheet is prepared by the preparation method described in any one of claim 1-9.
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