CN104078519A - Solar cell slice and fabrication method thereof - Google Patents
Solar cell slice and fabrication method thereof Download PDFInfo
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- CN104078519A CN104078519A CN201310104733.5A CN201310104733A CN104078519A CN 104078519 A CN104078519 A CN 104078519A CN 201310104733 A CN201310104733 A CN 201310104733A CN 104078519 A CN104078519 A CN 104078519A
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- solar battery
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 81
- 239000010703 silicon Substances 0.000 claims abstract description 81
- 229910052751 metal Inorganic materials 0.000 claims abstract description 79
- 239000002184 metal Substances 0.000 claims abstract description 79
- 239000000758 substrate Substances 0.000 claims abstract description 75
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000010936 titanium Substances 0.000 claims abstract description 62
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 62
- 230000005684 electric field Effects 0.000 claims abstract description 20
- 239000006117 anti-reflective coating Substances 0.000 claims description 44
- 238000002360 preparation method Methods 0.000 claims description 42
- 238000001704 evaporation Methods 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 19
- 230000008020 evaporation Effects 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000608 laser ablation Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 238000007738 vacuum evaporation Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 48
- 229910052709 silver Inorganic materials 0.000 description 46
- 239000004332 silver Substances 0.000 description 45
- 239000002002 slurry Substances 0.000 description 37
- 238000007639 printing Methods 0.000 description 23
- 229910052782 aluminium Inorganic materials 0.000 description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- 238000005245 sintering Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- 238000009713 electroplating Methods 0.000 description 13
- 239000004411 aluminium Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000010946 fine silver Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- -1 flood Substances 0.000 description 1
- 238000007654 immersion Methods 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000009466 transformation 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
- H01L31/0224—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
-
- 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
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Sustainable Development (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Life Sciences & Earth Sciences (AREA)
- Power Engineering (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a solar cell slice and a fabrication method thereof. The solar cell slice comprises a silicon substrate slice, a positive-surface electrode on the front surface of the silicon substrate slice, a back electric field on the back surface of the silicon substrate and a back electrode electrically communicated with the back electric field, wherein the front surface of the silicon substrate slice comprises a non-antireflection film region, and the positive-surface electrode comprises a metal titanium layer arranged on the surface of the non-antireflection film region and a conductive metal layer arranged on the surface of the metal titanium layer. The positive-surface electrode is high in fine density, line broken is difficult to happen, the solar cell slice is difficult to strip and fall off, the resistance when the cells are connected in series is low, high fill factor is achieved, the photoelectric conversion efficiency of the cell is high, and the cost is low.
Description
Technical field
The present invention relates to area of solar cell, more particularly, the present invention relates to a kind of solar battery sheet and preparation method thereof.
Background technology
Solar energy is as a kind of green energy resource, inexhaustible, pollution-free with it, not be more and more subject to people's attention by the advantages such as region resource limitation.Existing silica-based solar cell is generally by being printed on the electrocondution slurry that contains conductive metal powder, glass dust and organic carrier on silicon substrate, is dried and fires to prepare electrode and back surface field.The backplate of solar cell silicon substrate is generally positive pole, and the electrocondution slurry of coating is generally back silver slurry; Back of the body surface is general to be applied containing aluminum conductive electric slurry, forms aluminium back surface field after sintering, and it can significantly improve open circuit voltage and the photoelectric conversion efficiency of battery; Front electrode is generally negative pole, by adopt silk screen printing front side silver paste after coated with antireflection film, then after crossing continuous tunnel furnace sintering, directly obtain positive silver electrode, front side silver paste is mainly formed by functional powder (metal powder), unorganic glass powder, organic carrier mix and blend rolling, metal powder, as conductive phase, is generally silver powder.Front electrode, at the sensitive surface of silicon substrate, affects the receptance of solar energy, and its depth-width ratio becomes emphasis and the focus of existing research raising cell photoelectric transformation efficiency.
Existing research is by first silk screen printing one deck Seed Layer silver slurry, carry out again photoinduction plating (LIP) silver process, preparation is by seed silver layer and electroplate the front electrode of the battery that silver layer jointly form, and the Seed Layer grid line of silk-screen is thin and short, after sintering as the conductive layer of plating fine silver, the front electrode volume resistance obtaining is low, fill factor, curve factor is high, and the photoelectric conversion efficiency of battery increases significantly, and also can reduce the consumption of conductive silver slurry, the electrosilvering cost that silver is starched is relatively low, has therefore also reduced cost.But also there are many problems in the preparation of existing silver-colored Seed Layer and silk-screen, affect its practical application, for example the fine and closely woven degree of the silver-colored Seed Layer grid line after silk-screen is difficult for reaching designing requirement, make the width of the secondary grid line of electrode after photoinduction is electroplated increase excessive, shading-area increases, and causes the short circuit current of battery to decline.
Existing also have further reduce costs, be plating fine copper technique by the process modification of electroplating fine silver, but all form silver-colored Seed Layer by printed silver electrocondution slurry in these techniques, and in electrocondution slurry, contain solvent and organic binder, in sintering process, there are solvent and organic binder to be heated volatile, can make to leave in sintering residue fine hole, in the follow-up use procedure of battery, copper atom likely contacts with silicon substrate through hole, thereby cause the photoelectric conversion efficiency of battery sharply to decline, affect the performance of cell piece.
Summary of the invention
The technical problem that the present invention solves is existing conductive silver slurry printing used for solar batteries while preparing Seed Layer grid line, in the Seed Layer grid line of preparation, contains a large amount of holes, affects the performance of solar battery sheet.Provide a kind of contain fine and closely woven degree higher, be difficult for occurring broken string phenomenon, be not easy to peel off the front electrode that comes off, solar battery sheet that resistance is low, fill factor, curve factor is high, the photoelectric conversion efficiency of battery is high, cost is low and preparation method thereof.
First object of the present invention is to provide a kind of solar battery sheet, this solar battery sheet comprises that silicon substrate sheet, the front electrode of silicon substrate sheet front surface, silicon substrate sheet carry on the back surperficial back of the body electric field and the back electrode with back of the body electric field conducting, wherein, silicon substrate sheet front surface is containing having or not antireflective coating district, described front electrode to comprise to be positioned at without the layer of titanium metal on surface, antireflective coating district and being positioned at the conductive metal layer on layer of titanium metal surface.
Second object of the present invention is to provide a kind of preparation method of solar battery sheet, be included in silicon substrate sheet front surface and prepare front electrode, surperficial back of the body electric field and the back electrode with the conducting of back of the body electric field prepared of the silicon substrate sheet back of the body, wherein, the preparation of front electrode is included in silicon substrate sheet front surface and prepares without antireflective coating district, after preparing layer of titanium metal without the surface in antireflective coating district, then prepare conductive metal layer on layer of titanium metal surface.
Wherein, the surface preparation of the silicon substrate sheet back of the body is carried on the back electric field and is adopted and well known to a person skilled in the art the whole bag of tricks preparation with the back electrode of back of the body electric field conducting, can be before silicon substrate sheet front surface is prepared front electrode, also can be after silicon substrate sheet front surface is prepared front electrode, the present invention limit its order.
Titanium-copper compound electric polar curve even compact that the present invention makes, smooth surface, has particularly greatly reduced the width that battery performance is affected to the secondary grid line of larger electrode, and the series resistance of battery reduces, short circuit current and fill factor, curve factor increase, and the photoelectric conversion efficiency of battery is improved.The adhesive strength of electrode wires and silicon substrate sheet and all stronger with the weld strength of photovoltaic welding belt, and titanium and to prepare the cost of titanium layer low, greatly reduce the cost of manufacture of battery, and technique is simple, easily realizes.
Brief description of the drawings
Fig. 1 is the part section structural representation of solar battery sheet of the present invention.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, 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, is not intended to limit the present invention.
The invention provides a kind of solar battery sheet, this solar battery sheet comprises that silicon substrate sheet, the front electrode of silicon substrate sheet front surface, silicon substrate sheet carry on the back surperficial back of the body electric field and the back electrode with back of the body electric field conducting, wherein, at silicon substrate sheet front surface containing having or not antireflective coating district, front electrode to comprise to be positioned at without the layer of titanium metal on surface, antireflective coating district and being positioned at the conductive metal layer on layer of titanium metal surface.
Wherein, silicon substrate sheet, back of the body electric field and back electrode are conventionally known to one of skill in the art, do not repeat them here.
Wherein, without antireflective coating district, the present invention refers to the region that there is no antireflective coating on silicon substrate sheet surface, can be not prepare in advance antireflective coating in silicon substrate sheet surface element subregion, for example put into behind mould or mask shielding part subregion, then do plasma enhanced chemical vapor deposition method (PECVD) coated with antireflection film.The present invention preferably forms without antireflective coating district by the antireflective coating of removing silicon substrate sheet surface, and what generally form is to need preparation to cover the region of front electrode without antireflective coating district.
The present invention is preferably containing heavily doped selective emission area without antireflective coating district, layer of titanium metal is positioned at surface, heavily doped selective emission area, wherein, preferably, heavily doped selective emission area is by phosphorus being diffused into the formation of silicon substrate sheet without antireflective coating district, increase the conductivity of layer of titanium metal, reduced the contact resistance of layer of titanium metal and silicon substrate, improved the electricity conversion of solar battery sheet.In better situation, preferably, the sheet resistance of heavily doped selective emission area is 10 ~ 30 Ω/.
Preferably, the height of layer of titanium metal is 0.1 ~ 3.0 μ m, and width is 5.0 ~ 25 μ m; Further preferably, the height of layer of titanium metal is 0.1 ~ 2.5 μ m, and width is 5.0 ~ 25 μ m; Further preferred, height 0.3 ~ 1.5 μ m of layer of titanium metal, width is 10 ~ 20 μ m; Further preferred, the height of layer of titanium metal is 0.3 ~ 1.0 μ m, and width is 10 ~ 20 μ m, can further optimize the overall volume resistance of electrode wires, also can avoid the phenomenon that breaks, and optimizes the performance of electrode.Wherein, conductive metal layer the present invention is simple metal layer, can be electroplated metal layer, plated metal kind the present invention do not limit, such as copper, silver etc., preferably, conductive metal layer is copper layer, conductivity is high, good welding performance, has good combination with titanium layer, and the cohesive force on titanium layer is also strong, especially the price of metallic copper is low, can reduce the cost of battery.
Preferably, the height of copper layer is 5.0 ~ 15 μ m, is preferably further highly 7.0 ~ 12 μ m, further optimize the overall volume resistance of electrode wires, optimize the width that electrode wires covers, optimize the absorption photon number of battery, also can obtain more excellent control technique, enhance productivity simultaneously.
Generally, front electrode comprises main grid line, the secondary grid line that is pooled to main grid line with by solar battery front side electric current and be connected with main grid line, wherein, number the present invention of main grid line and secondary grid line does not limit, and is generally multiplely, between general main grid line, is parallel to each other, secondary grid line is vertical with main grid line, is connected with nearer main grid line.General main grid line is wider, require lower, secondary grid line is many and narrow, its height and width are larger on the impact of battery, and the present invention is preferred, and the height of secondary grid line is 10 ~ 20 μ m, width is 25 ~ 50 μ m, further optimize the light-receiving area of battery, improved the electricity conversion of solar cell, also reduced cost simultaneously.
The method that the present invention is preferably formed layer of titanium metal is evaporation, easily realization and easy to control, and the titanium layer even compact obtaining, its easier barrier layer as metal levels such as subsequent copper layers, can prevent that metallic copper atom etc. from infiltrating through silicon substrate, and form the complex centre of photo-generated carrier, affect the performance of battery.Forming the method for conductive metal layer is that photoinduction is electroplated, and process, easily realize, and the conductive metal layer performance of preparation is excellent, has good cohesive force and lower volume resistance with titanium layer.
The present invention provides the preparation method of above-mentioned solar battery sheet simultaneously, be included in silicon substrate sheet front surface and prepare front electrode, surperficial back of the body electric field and the back electrode with the conducting of back of the body electric field prepared of the silicon substrate sheet back of the body, wherein, the preparation of front electrode is included in silicon substrate sheet front surface and prepares without antireflective coating district, after preparing layer of titanium metal without the surface in antireflective coating district, then prepare conductive metal layer on layer of titanium metal surface.
The present invention preferably comprises in the preparation of silicon substrate sheet front surface the antireflective coating of removing silicon substrate sheet front surface by the method for laser ablation without the method in antireflective coating district, wherein, method, the Step By Condition of laser ablation are known to the skilled person, and do not repeat them here.
Preferably, also containing heavily doped selective emission area without antireflective coating district, heavily doped selective emission area can be when preparation is without antireflective coating district, also can be after preparation is without antireflective coating district, when silicon substrate sheet front surface preparation is without antireflective coating district and/or be also included in without antireflective coating district and prepare heavily doped selective emission area afterwards, prepare layer of titanium metal on the surface of heavily doped selective emission area more afterwards.The present invention is preferred, when the preparation of silicon substrate sheet front surface is without antireflective coating district, prepare heavily doped selective emission area, step can comprise, at least need the part surface of preparing front electrode to adhere to solution containing phosphate at silicon substrate sheet front surface, afterwards this part surface is carried out to laser ablation, under the condition of laser ablation, when removing antireflective coating, phosphorus atoms is diffused in silicon substrate sheet and form heavy doping.Wherein, adhere to the surface of the silicon substrate sheet of solution containing phosphate, can be that whole silicon substrate sheet front surface can be also the part surface of silicon substrate sheet, the present invention does not limit, for example, the method such as can adopt printing, roll-in, scrape slurry, flood, spray and lift is at whole silicon substrate sheet front surface coating solution containing phosphate, also the part surface that can first not need preparation to cover front electrode by mould or mask etc. to silicon substrate sheet hides, and covers the part surface spraying solution containing phosphate of front electrode at exposed need.The present invention is preferred, when the preparation of silicon substrate sheet front surface is without antireflective coating district, prepare heavily doped selective emission area, step is included in silicon substrate sheet front surface and applies solution containing phosphate, cover the surface that does not need to prepare front electrode by mask, the exposed surface of being prepared by need to front electrode carries out laser ablation.Wherein, mask the present invention do not limit, for example, can be metal mask.Wherein, the openwork part of metal mask is suitable with front electrode shape.
Preferably, solution containing phosphate is phosphoric acid solution, and the mass concentration of described phosphoric acid solution is 1.0 ~ 3.0wt%.
Preferably, comprise evaporation titanium in the method for preparing layer of titanium metal without the surface in antireflective coating district.In better situation, preferably, evaporation titanium is vacuum evaporation, and the equipment of vacuum evaporation is known to the skilled person, and preferably, the condition of described vacuum evaporation is: vacuum background air pressure is 10
-3pa, the air pressure of evaporation is 0.5 × 10
-3~ 2.0 × 10
-3pa, evaporating temperature when evaporation is 950 ~ 1050 DEG C.
Preferably, the method for preparing conductive metal layer on layer of titanium metal surface comprises that photoinduction electroplates.Preferably, conductive metal layer is copper layer, and photoinduction is electroplated as photoinduction electro-coppering, and electroplating time, current density, copper ion concentration etc. can design according to the copper layer height of electroplating.Photoinduction electroplating technique adopts and well known to a person skilled in the art various photoinduction electroplating technologies, for example evaporation can there be is the silicon substrate sheet of layer of titanium metal to put into photoinduction and electroplate the anode of electrolysis tank (German Schmid company produce) as plating, using fine copper rod as the negative electrode of electroplating, electrolyte used is copper sulfate solution, preferably, 40 ~ 65 DEG C of the temperature of electrolyte, Cu in electroplate liquid
2+mass concentration be 80 ~ 180g/L, preferably, the cathode-current density that photoinduction is electroplated is 2.0 ~ 10A/dm
2.
Preferably, after preparation layer of titanium metal, before conductive metal layer is prepared on layer of titanium metal surface, also comprise that the silicon substrate sheet to containing layer of titanium metal carries out high-temperature process, the temperature of described high-temperature process is 500 ~ 600 DEG C, and the time is 5.0 ~ 10min, the Titanium after can enhanced deposition and the adhesive force of silicon base, make layer of titanium metal and silicon base form good ohmic contact, and make layer of titanium metal finer and close evenly.
Wherein, silicon substrate sheet back of the body surface preparation back of the body electric field and with the method for the back electrode of back of the body electric field conducting, can adopt and well known to a person skilled in the art various preparation methods, for example, can be the back of the body surface printing back silver electrocondution slurry at silicon substrate sheet, after oven dry, remaining part prints aluminum back-surface-field conductive paste overleaf again, after oven dry, enter together continuous tunnel furnace sintering, back of the body silver slurry and back of the body aluminium paste have formed respectively backplate and the back of the body electric field of solar cell.Wherein, back silver electrocondution slurry and aluminum back-surface-field conductive paste adopt various back silver electrocondution slurries known in those skilled in the art and aluminum back-surface-field conductive paste.Below by specific embodiment, the invention will be further described.
Embodiment 1
(1) the polysilicon chip specification adopting is: 156 × 156mm.Before thickness is 200 μ m(corrosion), before printing, thickness is 180 μ m.Silicon wafer wool making, PN junction processed, employing PECVD method are being plated to silicon nitride anti-reflecting film.First adopt silk screen printing back silver slurry (the PV505 silver slurry of Dupont company), dry, in the remaining shady face part of printing back of the body silver slurry, printing back field aluminum paste (Taiwan large standing grain science and technology 108C aluminium paste), after oven dry, after continuous tunnel furnace sintering, obtain possessing the silicon substrate sheet of silver-colored back electrode and aluminium back surface field.
As shown in Figure 1.
(2) prepare heavily doped selective emitter district 4
Design front electrode comprises three main grids, contains antireflective coating 1 in the silicon substrate sheet 5(of above-mentioned preparation front face surface) phototropic face rotary coating one deck concentration is 2.0wt% phosphoric acid solution; And then cover upper mask, and wherein, mask is metallic nickel hollowed-out board, its vacancy section shape is identical with front electrode; Adopt laser ablation hollow part silicon substrate sheet 5 positive exposed antireflective coatings 1, make phosphorus diffuse in silicon substrate sheet 5 simultaneously, forming sheet resistance at laser ablation place is the heavily doped selective emitter of 20 ~ 25 Ω/ district 4.
(3) evaporation titanium
The mode plated metal titanium that adopts vacuum evaporation, in vacuum chamber, vacuum background pressure is 10
-3pa, keeps air pressure 1.0 ~ 1.2 × 10 in the process of evaporation
-3pa, evaporating temperature is 1000 ± 10 DEG C, and the evaporation time is 11min, and the height of the secondary grid line layer of titanium metal 3 obtaining is 0.50 ~ 0.70 μ m, and width is 10 ~ 12 μ m.
(4) high-temperature process
Silicon substrate sheet 5 after plated metal titanium layer 3 is put into the annealing furnace of 550 DEG C, after insulation 8min, taken out.
(5) photoinduction electro-coppering
Adopt photoinduction electroplating technology plated metal copper layer 2 in layer of titanium metal 3, electroplate liquid adopts copper sulfate solution, and electrolyte temperature is 55 ± 2 DEG C, Cu
2+mass concentration is 100g/L, cathode-current density 4.5A/dm
2, electroplating time is 8.5min, then goes out electrolysis tank, obtains cell piece with hot blast drying.The total height of the secondary grid line of front electrode that test obtains is 10 ~ 13 μ m, and overall width is 20 ~ 25 μ m.It is S1 that the present embodiment obtains solar cell sample.
Embodiment 2
Adopt the method step identical with embodiment 1 to prepare solar cell sample S2, the time of the middle evaporation of step (3) that different is is 8min, and the secondary grid line layer of titanium metal height making is 0.20 ~ 0.40 μ m, and width is 8.0 ~ 10 μ m.The total height of the secondary grid line of front electrode that test obtains is 9.0 ~ 12 μ m, and overall width is 18 ~ 23 μ m.
Embodiment 3
Adopt the method step identical with embodiment 1 to prepare solar cell sample S3, the time of the middle evaporation of step (3) that different is is 30min, and the secondary grid line layer of titanium metal height making is 1.4 ~ 1.6 μ m, and width is 15 ~ 18 μ m.The total height of the secondary grid line of front electrode that test obtains is 12 ~ 15 μ m, and overall width is 25 ~ 30 μ m.
Embodiment 4
Adopt the method step identical with embodiment 1 to prepare solar cell sample S4, the time of the middle evaporation of step (3) that different is is 60min, and the secondary grid line layer of titanium metal height making is 2.7 ~ 3.0 μ m, and width is 20 ~ 25 μ m.The total height that test obtains the secondary grid line of front electrode is 13 ~ 16 μ m, and overall width is 40 ~ 45 μ m.
Embodiment 5
Adopt the method step identical with embodiment 1 to prepare solar cell sample S5, the time of the middle photoinduction electro-coppering of step (5) that different is is 13min.The total height that test obtains the secondary grid line of front electrode is 15 ~ 18 μ m, and overall width is 45 ~ 50 μ m.
Embodiment 6
Adopt the method step identical with embodiment 1 to prepare solar cell sample S6, the concentration of the phosphoric acid solution that different is uses in step (2) is 3.0wt%, and at laser ablation place, formation sheet resistance is the heavily doped selective emitter of 10 ~ 15 Ω/ district.The total height of the secondary grid line of front electrode that test obtains is 10 ~ 13 μ m, and overall width is 20 ~ 25 μ m.
Embodiment 7
Adopt the method step identical with embodiment 1 to prepare solar cell sample S7, different is without the high-temperature process in step (4).The total height of the secondary grid line of front electrode that test obtains is 10 ~ 13 μ m, and overall width is 20 ~ 25 μ m.
Comparative example 1
The polysilicon chip specification adopting is: 156 × 156mm.Before thickness is 200 μ m(corrosion), before printing, thickness is 180 μ m.Silicon wafer wool making, PN junction processed, employing PECVD method are being plated to silicon nitride anti-reflecting film.First adopt 280 object silk screen printing back silver slurries (the PV505 silver slurry of Dupont company), the printing weight in wet base of back of the body silver slurry is 35 ~ 50mg, dry, in the remaining shady face part of printing back of the body silver slurry, the same 280 order printing back field aluminum pastes (Taiwan large standing grain science and technology 108C aluminium paste) that adopt, the printing weight in wet base of aluminium paste is 1.2 ~ 1.4g, dry, then adopt 400 orders, live width is that the half tone of 60 μ m is printed on phototropic face silver slurry (the 8521A silver slurry of Samsung company) on the phototropic face of silicon substrate sheet, printing weight in wet base is 105 ~ 125mg, enter and in continuous tunnel furnace, dry sintering, preheat temperature is 200 ~ 400 DEG C, peak temperature is 910 ~ 930 DEG C, the whole time that crosses continuous tunnel furnace is about 2 minutes, peak value sintering time is about 1 second, obtain being printed with the gate electrode line of front side silver paste, the secondary grid line height that test obtains after sintering is 10 ~ 14 μ m, width is 70 ~ 80 μ m.Remember that this cell piece is DS1.
Comparative example 2
(1) the polysilicon chip specification adopting is: 156 × 156mm.Before thickness is 200 μ m(corrosion), before printing, thickness is 180 μ m.Silicon wafer wool making, PN junction processed, employing PECVD method are being plated to silicon nitride anti-reflecting film.First adopt 280 order silk screen printing back silver slurries (the PV505 silver slurry of Dupont company), the printing weight in wet base of back of the body silver slurry is 35 ~ 50mg, dry, in the remaining shady face part of printing back of the body silver slurry, the same 280 order printing back field aluminum pastes (Taiwan large standing grain science and technology 108C aluminium paste) that adopt, the printing weight in wet base of aluminium paste is 1.2 ~ 1.4g, dry, then adopt 400 orders, live width is that the half tone of 45 μ m is printed on phototropic face silver slurry (the 17F silver slurry of Dupont company) on the phototropic face of silicon substrate sheet as seed silver slurry, printing weight in wet base is 60 ~ 70mg, enter and in continuous tunnel furnace, dry sintering, preheat temperature is 200 ~ 400 DEG C, peak temperature is 910 ~ 930 DEG C, the whole time that crosses continuous tunnel furnace is about 2 minutes, peak value sintering time is about 1 second, obtain being printed with the gate electrode line of Seed Layer silver slurry, the silver-colored line height that test obtains after sintering is 6.0 ~ 8.0 μ m, width is 60 ~ 70 μ m.
(2) adopt plated metal silver on the seed silver layer of photoinduction electroplating technology after sintering, electroplate liquid adopts AgNO
3solution, electrolyte temperature is 35 ± 2 DEG C, Ag
+concentration is 30g/L, cathode-current density 4A/dm
2, electroplating time is 5min, then goes out electrolysis tank, the cell piece making with hot blast drying.The height that records plating silver layer is 5.0 ~ 7.0 μ m, and the total height of the secondary grid line of cell piece front electrode is 11 ~ 15 μ m, and overall width is 70 ~ 80 μ m, remembers that this cell piece is DS2.
Comparative example 3
(1) the polysilicon chip specification adopting is: 156 × 156mm, before thickness is 200 μ m(corrosion), before printing, thickness is 180 μ m.Silicon wafer wool making, PN junction processed, employing PECVD method are being plated to silicon nitride anti-reflecting film.First adopt 280 order silk screen printing back silver slurries (the PV505 silver slurry of Dupont company), the printing weight in wet base of back of the body silver slurry is 35 ~ 50mg, dry, in the remaining shady face part of printing back of the body silver slurry, the same 280 order printing back field aluminum pastes (Taiwan large standing grain science and technology 108C aluminium paste) that adopt, the printing weight in wet base of aluminium paste is 1.2 ~ 1.4g, dry, then adopt 400 orders, live width is that the half tone of 45 μ m is printed on phototropic face silver slurry (the 17F silver slurry of Dupont company) on the phototropic face of silicon substrate sheet as seed silver slurry, printing weight in wet base is 60 ~ 70mg, enter and in continuous tunnel furnace, dry sintering, preheat temperature is 200 ~ 400 DEG C, peak temperature is 910 ~ 930 DEG C, the whole time that crosses continuous tunnel furnace is about 2 minutes, peak value sintering time is about 1 second, obtain being printed with the gate electrode line of Seed Layer silver slurry, the silver-colored line height that test obtains after sintering is 6.0 ~ 8.0 μ m, width is 60 ~ 70 μ m.(2) adopt plated metal copper on the seed silver layer of photoinduction electroplating technology after sintering, electroplate liquid adopts copper sulfate solution, and electrolyte temperature is 55 ± 2 DEG C, Cu
2+concentration is 100g/L, cathode-current density 4.5A/dm
2, electroplating time is 4.0min, then goes out electrolysis tank, obtains cell piece sample with hot blast drying, the height that records copper electroplating layer is 5.0 ~ 7.0 μ m.The total height of the secondary grid line of cell piece front electrode is 11 ~ 15 μ m, and overall width is 70 ~ 80 μ m, remembers that this cell piece is DS3.
performance test
Surface appearance: adopt 5 ~ 10 times of magnifying glasses to observe front electrode surface appearances, whether smooth, have or not plot point and hole.If smooth surface, without the phenomenon such as plot point and hole, is designated as OK, otherwise is designated as NG.
Short circuit current I
sC(A)
,series resistance R
s(m Ω), fill factor, curve factor FF, electricity conversion Eta: the solar battery sheet sample that adopts single flash operation simulation test instrument to prepare embodiment and comparative example is tested, and test condition is standard test condition (STC): light intensity: 1000W/m
2; Spectrum: AM1.5; Temperature: 25 DEG C.
Weld strength (N): select victory footpath between fields, Shanghai 2*0.2mm tin lead welding band, by Henkel X32-10I type scaling powder immersion post-drying, then carry out manual welding at 330 DEG C of main grid lines to electrode.After cell piece is naturally cooling, the electrode that uses mountain degree SH-100 puller system to connect along 135 ° of direction butt welding carries out tensile test.
Test result is as table 1.
Table 1
| Sample | Surface appearance | I SC(A) | Rs(mΩ) | FF | Eta | Weld strength (N) |
| S1 | OK | 8.643 | 1.115 | 80.98 | 17.84% | 6.58 |
| S2 | OK | 8.669 | 1.454 | 80.50 | 17.78% | 5.75 |
| S3 | OK | 8.651 | 1.521 | 80.40 | 17.74% | 6.81 |
| S4 | OK | 8.633 | 1.292 | 80.52 | 17.71 % | 7.01 |
| S5 | OK | 8.648 | 1.869 | 80.21 | 17.68% | 6.67 |
| S6 | OK | 8.645 | 1.910 | 80.16 | 17.63% | 6.47 |
| S7 | OK | 8.640 | 1.912 | 80.13 | 17.61% | 5.48 |
| DS1 | OK | 8.516 | 2.203 | 79.77 | 17.50% | 5.45 |
| DS2 | OK | 8.552 | 2.121 | 79.78 | 17.55% | 5.13 |
| DS3 | OK | 8.482 | 2.481 | 79.22 | 17.21% | 4.23 |
Titanium-copper compound electric polar curve even compact that the present invention makes, smooth surface, the secondary grid line width of electrode greatly reduces, shading-area reduces, and the series resistance of battery reduces, short circuit current, especially fill factor, curve factor has by a relatively large margin increases, and the photoelectric conversion efficiency of battery gets a promotion.The weld strength of electrode wires and photovoltaic welding belt is also stronger, and titanium and to prepare the cost of titanium layer low, greatly reduce the cost of manufacture of battery, and technique is simple, easily realizes.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (22)
1. a solar battery sheet, described solar battery sheet comprises that silicon substrate sheet, the front electrode of silicon substrate sheet front surface, silicon substrate sheet carry on the back surperficial back of the body electric field and the back electrode with back of the body electric field conducting, it is characterized in that, described silicon substrate sheet front surface is containing having or not antireflective coating district, described front electrode to comprise to be positioned at without the layer of titanium metal on surface, antireflective coating district and being positioned at the conductive metal layer on layer of titanium metal surface.
2. solar battery sheet according to claim 1, is characterized in that, described antireflective coating formation of passing through to remove silicon substrate sheet surface without antireflective coating district.
3. solar battery sheet according to claim 1, is characterized in that, describedly contains heavily doped selective emission area without antireflective coating district, and described layer of titanium metal is positioned at surface, heavily doped selective emission area.
4. solar battery sheet according to claim 3, is characterized in that, described heavily doped selective emission area is by diffusing into the formation of silicon substrate sheet without antireflective coating district by phosphorus.
5. solar battery sheet according to claim 3, is characterized in that, the sheet resistance of described heavily doped selective emission area is 10 ~ 30 Ω/.
6. solar battery sheet according to claim 1, is characterized in that, the height of described layer of titanium metal is 0.1 ~ 3.0 μ m, and width is 5.0 ~ 25 μ m.
7. solar battery sheet according to claim 6, is characterized in that, the height of described layer of titanium metal is 0.3 ~ 1.0 μ m, and width is 10 ~ 20 μ m.
8. solar battery sheet according to claim 1, is characterized in that, described conductive metal layer is copper layer.
9. solar battery sheet according to claim 8, is characterized in that, the height of described copper layer is 5.0 ~ 15 μ m.
10. solar battery sheet according to claim 1, it is characterized in that, described front electrode comprises main grid line and solar battery front side electric current is pooled to the secondary grid line that main grid line is connected with main grid line, and the height of described secondary grid line is 10 ~ 20 μ m, and width is 25 ~ 50 μ m.
11. solar battery sheets according to claim 1, is characterized in that, the method that forms layer of titanium metal is evaporation, and the method that forms conductive metal layer is that photoinduction is electroplated.
The preparation method of 12. 1 kinds of solar battery sheets, be included in silicon substrate sheet front surface and prepare front electrode, surperficial back of the body electric field and the back electrode with the conducting of back of the body electric field prepared of the silicon substrate sheet back of the body, it is characterized in that, the preparation of described front electrode is included in silicon substrate sheet front surface and prepares without antireflective coating district, after preparing layer of titanium metal without the surface in antireflective coating district, then prepare conductive metal layer on layer of titanium metal surface.
13. preparation methods according to claim 12, is characterized in that, the described antireflective coating of removing silicon substrate sheet front surface by the method for laser ablation that comprises without the method in antireflective coating district in silicon substrate sheet front surface preparation.
14. preparation methods according to claim 12, it is characterized in that, when silicon substrate sheet front surface preparation is without antireflective coating district and/or be also included in without antireflective coating district and prepare heavily doped selective emission area afterwards, after prepare layer of titanium metal on the surface of heavily doped selective emission area.
15. preparation methods according to claim 14, it is characterized in that, when the preparation of silicon substrate sheet front surface is without antireflective coating district, prepare heavily doped selective emission area, step is included in silicon substrate sheet front surface at least needs the part surface of preparing front electrode to adhere to solution containing phosphate, rear this part surface is carried out to laser ablation.
16. preparation methods according to claim 15, it is characterized in that, when the preparation of silicon substrate sheet front surface is without antireflective coating district, prepare heavily doped selective emission area, step is included in silicon substrate sheet front surface and applies solution containing phosphate, cover the surface that does not need to prepare front electrode by mask, the exposed surface of being prepared by need to front electrode carries out laser ablation.
17. preparation methods according to claim 16, is characterized in that, described solution containing phosphate is phosphoric acid solution, and the mass concentration of described phosphoric acid solution is 1.0 ~ 3.0wt%.
18. preparation methods according to claim 12, is characterized in that, comprise evaporation titanium in the method for preparing layer of titanium metal without the surface in antireflective coating district.
19. preparation methods according to claim 18, is characterized in that, described evaporation titanium is vacuum evaporation, and the vacuum background air pressure that the condition of described vacuum evaporation is evaporation is 10
-3pa, the air pressure of evaporation is 0.5 × 10
-3~ 2.0 × 10
-3pa, evaporating temperature when evaporation is 950 ~ 1050 DEG C.
20. preparation methods according to claim 12, is characterized in that, the method for preparing conductive metal layer on layer of titanium metal surface comprises photoinduction plating.
21. preparation methods according to claim 20, is characterized in that, described conductive metal layer is copper layer, described photoinduction is electroplated as photoinduction electro-coppering, described photoinduction electro-coppering electrolyte used is copper sulfate solution, 40 ~ 65 DEG C of the temperature of electrolyte, Cu in electroplate liquid
2+mass concentration be 80 ~ 180g/L, the cathode-current density that described photoinduction is electroplated is 2.0 ~ 10A/dm
2.
22. preparation methods according to claim 12, it is characterized in that, after preparation layer of titanium metal, before conductive metal layer is prepared on layer of titanium metal surface, also comprise that the silicon substrate sheet to containing layer of titanium metal carries out high-temperature process, the temperature of described high-temperature process is 500 ~ 600 DEG C, and the time is 5.0 ~ 10min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104362200A (en) * | 2014-10-30 | 2015-02-18 | 广东爱康太阳能科技有限公司 | Efficient crystalline silicon solar cell and production method thereof |
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| US11133426B2 (en) | 2014-11-28 | 2021-09-28 | Lg Electronics Inc. | Solar cell and method for manufacturing the same |
| US11239379B2 (en) | 2014-11-28 | 2022-02-01 | Lg Electronics Inc. | Solar cell and method for manufacturing the same |
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