CN103489951B - Two-sided black crystalline silicon high-efficiency solar cell - Google Patents
Two-sided black crystalline silicon high-efficiency solar cell Download PDFInfo
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- CN103489951B CN103489951B CN201310398371.5A CN201310398371A CN103489951B CN 103489951 B CN103489951 B CN 103489951B CN 201310398371 A CN201310398371 A CN 201310398371A CN 103489951 B CN103489951 B CN 103489951B
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- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 142
- 239000010703 silicon Substances 0.000 claims abstract description 142
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 33
- 239000011574 phosphorus Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 23
- 230000005693 optoelectronics Effects 0.000 claims abstract description 10
- 238000002161 passivation Methods 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 76
- 239000010410 layer Substances 0.000 claims description 76
- 239000005864 Sulphur Substances 0.000 claims description 65
- 239000013078 crystal Substances 0.000 claims description 51
- 239000011011 black crystal Substances 0.000 claims description 43
- 238000002360 preparation method Methods 0.000 claims description 31
- 238000009792 diffusion process Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 238000005260 corrosion Methods 0.000 claims description 16
- 230000007797 corrosion Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005083 Zinc sulfide Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 12
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 12
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 3
- 239000011241 protective layer Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 description 44
- 229910021418 black silicon Inorganic materials 0.000 description 42
- 239000000203 mixture Substances 0.000 description 25
- 239000002800 charge carrier Substances 0.000 description 21
- 238000005530 etching Methods 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 238000000708 deep reactive-ion etching Methods 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 150000004770 chalcogenides Chemical class 0.000 description 6
- 238000002679 ablation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0684—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells double emitter cells, e.g. bifacial solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0687—Multiple junction or tandem solar cells
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- 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
- Y02E10/544—Solar cells from Group III-V materials
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Abstract
The present invention is two-sided black crystalline silicon high-efficiency solar cell, solves and has manufacture of solar cells efficiency low the sixth of the twelve Earthly Branches, is unsuitable for large area and produces, the problem that photoelectric conversion efficiency is low.Comprise from upper surface to lower surface: double-layer reflection-decreasing film (4), front first negative electrode (5), absorb and fall into photosphere (3), mix phosphorus n-layer (2), the monocrystalline silicon piece (1) of P-type silicon base substrate, mix phosphorus n-layer (2), absorb and fall into photosphere (3), the second negative electrode (8), positive and negative electrode passivation separator (7), positive electrode (6), the double-edged of the monocrystalline silicon piece (1) of P-type silicon base substrate is mixed phosphorus n-layer (2) and absorbs the n falling into photosphere (3)
+layer combination forms height knot (n
+/ n ties), then form opto-electronic conversion (n with the crystalline silicon of the monocrystalline silicon piece (1) of P-type silicon base substrate
+/ n)/p structure, double-sided solar battery positive and negative forms two respective independently batteries.
Description
technical field:
The present invention relates to a kind of Can of utilization Liu ?the solar cell prepared of crystal silicon.
technical background:
In recent years, the fossil energy shortage such as traditional coal, oil, too much use fossil energy causes global warming, environmental pollution day by day serious, and the mankind are badly in need of finding reproducible green energy resource.Solar energy is inexhaustible, environmental protection, is expected to alternative traditional energy, and directly transform light energy can be become electric energy as important device-solar cell that solar energy uses.In recent years, crystal silicon solar energy battery obtains and develops fast, compares the solar cell of other type, and the technology of crystal silicon battery is comparatively ripe, and occupation rate of market reaches about 80%.At present, the conversion efficiency of monocrystaline silicon solar cell laboratory research reaches 24.7% [SolarEnergyMaterials & SolarCells.65 (2001)], the commercial battery efficiency of large-scale production is generally about 18%, want to realize civilian in a large number, still have that conversion efficiency is not high, price problem costly.Want to further develop crystal silicon solar batteries, the problem that first will solve how to pass through to improve the cost that conversion efficiency reduces battery.
From the absorption of battery to light, crystal silicon absorbs the wave band mainly visible light wave range of sunlight, the photon that the energy gap wavelength only having energy to be greater than silicon is less than 1.1 μm could produce charge carrier by absorption, and the infrared photon that wavelength is greater than 1.1 μm loses with the form of heat without contribution electric current substantially.By theory calculate and analysis, the energy being greater than the infrared light of 1.1 μm occupies more than 30% of solar energy gross energy, if the spectrum of this scope can be used, just can realize the raising of battery conversion efficiency.Calendar year 2001 Harvard University researcher Mazur lead research team utilize in the atmosphere of sulfur-bearing laser scanning crystalline silicon get Dao ?silicon, and Fa Xian ?silicon in the absorptivity of visible light wave range up to more than 99%, can 95% be reached at 1.1 μm to the near-infrared absorption within the scope of 2.5 μm to wavelength, widen the spectral absorption scope [APPLIEDPHYSICSLETTERS.78,13 (2001)] of silica-base material greatly.Utilize Can Liu ?the solar cell prepared of silicon to increase the absorption of near infrared spectrum be the important channel can improving conversion efficiency of solar cell.
The report utilizing black silicon to prepare photoelectric device and solar cell in recent years increases gradually, the black silicon utilizing femtosecond laser to prepare is had only to apply to the upper surface of battery as sunken photosphere, increase the absorption of near infrared band energy, the luminous energy that black silicon absorbs effectively is not converted into electric energy, the luminous energy major part absorbed is depleted; Or directly make black silicon at the back side of battery, be used for specially absorbing the infrared light through silicon chip, but cannot electric energy be effectively converted into by the carrier lifetime of absorption infrared photon generation is very short, cause the utilance of infrared energy lower.At present, mixing the black silicon microstructure of sulphur is both at home and abroad substantially all at H by femtosecond laser
2s, SF
6in atmosphere, ablation one step is formed, and the black silicon of formation is non-crystal structure mostly.Cause in the black silion cell prepared that carrier mobility is low, the life-span is short like this, and the series resistance R of battery
sgreatly.All only there is one side PN junction in the black silion cell of preparation, can not more effective absorption near infrared spectrum, can not be output current by the effective energy transformation of absorption rapidly.Femtosecond laser mixes that the black silicon area of sulphur is little, working (machining) efficiency is low.Carry out high-octane ablation with femtosecond laser and prepare black silicon, production efficiency is low, unfavorable to large area production and application.
Application number be 201010543469.1 invention (having application hereinafter referred to as the sixth of the twelve Earthly Branches) make dopant diffusion layer, micron light-absorption layer, nanometer antireflection layer respectively successively at the positive and negative of silicon-based substrate.This application adopts silicon dioxide or silicon nitride single antireflection film.In battery structure, antireflective coating uses individual layer silicon dioxide or silicon nitride, and the refractive index of silicon dioxide is 1.46, and the refractive index of silicon nitride is 1.97.The antireflecting light wave narrow range of monofilm, effect is not as good as double-layer compound film.
Have the sixth of the twelve Earthly Branches application just using black silicon as antireflection layer (absorbed layer), the black silicon formed without mask etching by DRIE to mix sulfur impurity concentration extremely low, it mixes sulphur concentration far below 10
16/ cm
3, sulphur can not form Effective Doping in black silicon layer, and black silicon is pure antireflection layer, does not have facilitation to transporting of charge carrier.Adopt DRIE without mask etching, what can not form high concentration mixes sulphur (n
+) layer, not there is the effective absorbability near infrared light.Adopt DRIE to prepare black silicon without mask etching and mainly use F
-ion pair silicon chip surface carries out physical chemistry etching and forms micro-nano structure, and in corrosion process, silicon there will not be molten condition, only have a small amount of sulphion to be adsorbed on silicon chip surface, and sulfur content is extremely low.The diameter of the nano-micro structure etched is 50nm to 1000nm, is highly 100nm to 10000nm, spacing 100nm to 1000nm, and the black silicon formed in the case, mainly as absorbed layer and antireflection layer, increases the absorption to visible ray.At SF
6carry out RIE in atmosphere to be etched with a small amount of sulphion and to mix in black silicon, very low (≤10 of sulfur content
16/ cm
3), the black Si semiconductor mixing sulphur can not be formed.Meanwhile, because low sulfur content cannot form the doped chalcogenide layer (n of high concentration
+layer), height knot (n can not be obtained
+/ n ties), make transporting of charge carrier in battery slack-off, affect carrier lifetime and battery conversion efficiency.This solar cell can only form opto-electronic conversion to visible ray, can not effectively absorb near infrared light and produce opto-electronic conversion.
The back side only has crystal silicon micron and black silicon nanometer absorption/antireflection layer, and the back side does not have PN junction, cannot be collected rapidly by the charge carrier that the energy of absorption changes into fast and effectively, very little to the contribution of increase photogenerated current, thus affects conversion efficiency.
Have the sixth of the twelve Earthly Branches application to adopt the black silicon of DRIE etching preparation only to have a small amount of sulphion to be adsorbed on silicon chip surface, but sulfur content is extremely low.The black silicon Main Function formed in the case is as absorbed layer and antireflection layer, increases the absorption to visible ray.Due to very low (≤10 of sulfur content in the black silicon of DRIE etching
16/ cm
3), the black Si semiconductor mixing sulphur can not be formed, the doped chalcogenide layer (n of high concentration cannot be formed
+layer), the height that black silicon and crystalline silicon form cannot be obtained in solar cell and tie (n
+/ n ties), make transporting of charge carrier in battery slack-off, affect carrier lifetime and battery conversion efficiency.This solar cell can only form opto-electronic conversion to visible ray, effectively can not absorb and carry out opto-electronic conversion near infrared light.The battery structure back side only has crystal silicon micron and black silicon nanometer to absorb antireflection layer, and the back side does not have PN junction, fast and effectively the energy of absorption cannot be changed into charge carrier and collect rapidly, very little to the contribution of increase photogenerated current, thus affects conversion efficiency.The black silicon of positive and negative respectively absorbs a sunlight, absorption number of times is few, and the charge carrier that the near infrared energy of back side absorption produces is difficult to be collected fast and effectively, and the charge carrier that the near infrared energy of back side absorption produces is difficult to be collected fast and effectively, thus affect the conversion efficiency of battery.
summary of the invention:
The object of this invention is to provide a kind of photoelectric conversion efficiency high, production efficiency is high, is suitable for the two-sided black crystalline silicon high-efficiency solar cell that large area is produced.
The present invention is achieved in that
Two-sided black crystalline silicon high-efficiency solar cell, comprises from upper surface to lower surface:
Front double-layer reflection-decreasing film 4, front first negative electrode 5, front absorb sunken photosphere 3, phosphorus n-layer 2 is mixed in front, P-type silicon base substrate 1, reverse side mix phosphorus n-layer 2, reverse side absorbs and falls into photosphere 3, reverse side second negative electrode 8, reverse side positive and negative electrode protective layer 7, reverse side positive electrode 6, and the positive and negative of P-type silicon base substrate 1 is mixed phosphorus n-layer 2 and absorbed with positive and negative the n falling into photosphere 3
+layer combination forms height knot (n
+/ n ties), then form opto-electronic conversion (n with P-type silicon base substrate 1
+/ n)/p structure, form two respective independently batteries at double-sided solar battery positive and negative.
It is that crystalline silicon is placed in chemical corrosion liquid corrosion preparation " pyramid " matte that described positive and negative absorbs the preparation falling into photosphere 3, then is positioned over and comprises SF
6utilize nanosecond laser to mix sulphur in the vacuum chamber of atmosphere and form black crystal silicon, laser energy density is selected at crystal silicon melting Near Threshold, LASER Light Source pulse wavelength is 532nm, repetition rate is 10Hz, the energy adopting laser is 3-10mJ, make silicon face 0.5 μm to 2 μm degree of depth be in molten condition to carry out mixing sulphur and form black crystal silicon, mix the concentration of sulphur 10
19-10
21/ cm
3.What positive and negative mixed phosphorus n-layer 2 mixes phosphorus impurities concentration 10
17-10
19/ cm
5,
Described front double-layer reflection-decreasing film 4 is made up of zinc sulphide and magnesium fluoride, and the thickness of zinc sulphide is between 20-100nm, and the thickness of magnesium fluoride is between 50-250nm.
First mixing phosphorus N-type layer 2 surface at positive and negative utilizes alkaline solution to etch formation " pyramid " structure, the height of " pyramid " structure is 1 μm to 20 μm, " pyramid " bottom lengths 2 μm-30 μm, then recycles nanosecond laser and forms the sunken photosphere 3 of positive and negative absorption in " pyramid " upper ablation.
What two reverse side second negative electrodes 8 and the reverse side positive electrode 6 that are symmetry axis with reverse side positive electrode 6 had a gap becomes interdigitated structure, and the pectinate texture of reverse side positive electrode extends to battery lower surface and covers whole battery lower surface, as cell backside mirror field.
Its preparation method comprises the following steps:
Step 1: be that monocrystalline silicon piece P-type silicon base substrate 1 between 200 μm to 500 μm is positioned in alkaline solution and carries out anisotropic etch by thickness, the matte characteristic preparing positive and negative is substantially identical, in matte " pyramid " height between 1 μm-20 μm, " pyramid " bottom lengths 2 μm-30 μm;
Step 2: in diffusion furnace, positive and negative for P-type silicon base substrate 1 diffusion into the surface is formed PN junction structure.P-type silicon base substrate 1 is the monocrystalline silicon piece of P type, and resistivity is 1-10 Ω .cm, and controlling thickness during diffusion is between 0.3 μm to 3 μm, and the concentration of mixing phosphorus is 10
17-10
19/ cm
3;
Step 3: utilize nanosecond laser comprising SF
6atmosphere in will mix phosphorus n-layer 2 ablation and reach and mix sulphur, form the black crystal silicon micro-structural of mixing sulphur in crystal silicon positive and negative N-type region with this, the black crystal silicon of silicon chip positive and negative and crystalline silicon are formed just ties micro-structural.Height knot accelerates the motion of charge carrier, is effectively separated the electronics-hole pair produced, and black crystal silicon layer increases absorption more than 1.1 μm near infrared energy, reaches the absorption increasing solar spectrum scope;
Step 4: pass through PECVD deposit silicon dioxide or silicon nitride passivation at the lower surface of battery;
Step 5: make electric front negative electrode, makes reverse side pectination positive and negative electrode;
Step 6: the process of electrode metal, is through high temperature sintering, protects under the atmosphere of nitrogen, obtains Ohm contact type electrode;
Step 7: at front crystal silicon surface vacuum deposit double layer antireflection coating, double layer antireflection coating is made up of zinc sulphide and magnesium fluoride, and the thickness of zinc sulphide is between 20-100nm, and the thickness of magnesium fluoride is between 50-250nm.
The present invention relates to a kind of structure and preparation method of two-sided black crystal silicon solar batteries, crystal silicon positive and negative surface use two-step method by nanosecond laser technology prepare Can Liu ?crystal silicon, carry out large area production.Two-step method prepares mobility and the life-span that black crystal silicon effectively improves charge carrier, mix the black crystal silicon of sulphur and crystal silicon to form height and tie, height knot formed surperficial field energy effectively by electronics-hole to separation, thus improve the electric current of battery, utilize the energy of the black crystal silicon PN junction of tow sides and back reflection field re-absorption effect visible ray and near infrared band, reach two-sided broad absorption.Well solve conventional crystalline silicon battery absorption solar energy spectral limit narrower, effectively can not convert thereof into the problem of electric current after improving black silion cell absorb photons, reach the object improving solar cell photoelectric conversion efficiency.
Nanosecond laser is comprising SF
6atmosphere in ablation silicon face reach and mix sulphur, the absorption of the black silicon obtained except having more than 99% to solar spectrum energy, especially the near infrared energy of 1.1 μm to 2.5 μm is had to the absorption of more than 95%.In addition, black crystal silicon layer (n prepared by sulphur is mixed by nanosecond laser
+layer) mix the concentration of sulphur 10
19-10
21/ cm
3, N-type crystal silicon layer mixes phosphorus impurities concentration 10
17-10
19/ cm
3, mix the black crystal silicon layer of sulphur and N-type crystal silicon and combine and form height and tie (n
+/ n ties).In the shape battery pair of height knot, charge carrier transports the effect playing acceleration, reduce the compound of charge carrier, relatively without the battery of height knot, the existence of height knot effectively can increase the photogenerated current of solar cell, significantly improves the voltage of the solar cell in full solar spectrum wavelength band.
The invention solves the problem that black silicon area is little, working (machining) efficiency is low that femtosecond laser mixes sulphur.Preparing black silicon by nanosecond laser in a vacuum chamber can by passing into the SF of vacuum chamber
6the air pressure size of gas controls the content mixing sulphur impurity of the black silicon of preparation, and the concentration of sulphur is 10
19-10
21/ cm
3, what can form high concentration mixes sulphur n
+type layer, the doped chalcogenide layer n of this high concentration
+the n-layer of mixing phosphorus with crystal silicon forms height and ties (n
+/ n ties), be conducive to transporting of charge carrier in battery, this height knot can realize significantly improving of open circuit voltage in the full spectral region of the sun.
Have the sixth of the twelve Earthly Branches in application battery structure, only using black silicon as antireflection layer (absorbed layer), the black silicon formed without mask etching by DRIE to mix sulfur impurity concentration extremely low, it mixes sulphur concentration far below 10
16/ cm
3, sulphur can not form Effective Doping in black silicon layer, and black silicon is pure antireflection layer, does not have facilitation to transporting of charge carrier.
It is comprising SF by nanosecond laser that the black crystal silicon of positive and negative of the present invention absorbs sunken photosphere
6large area in atmosphere, mix the black crystal silicon micro-structural that sulphur formed fast, the preparation of black crystal silicon is that crystalline silicon is placed in chemical corrosion liquid corrosion preparation " pyramid " matte, then is positioned over and comprises SF
6utilize nanosecond laser to mix sulphur in the vacuum chamber of atmosphere and form black crystal silicon, laser energy density is selected at crystal silicon melting Near Threshold, LASER Light Source pulse wavelength is 532nm, repetition rate is 10Hz, the energy adopting laser is 3-10mJ, make silicon face to 0.5 μm or 2 μm of degree of depth be in molten condition to carry out mixing sulphur and form black crystal silicon, mix the concentration of sulphur 10
19-10
21/ cm
3, this black crystal silicon has efficient absorption (absorptivity is greater than 95%) to the full spectrum of the sun within the scope of 0.3 μm to 2.5 μm.Carry out line sweep by nanosecond laser when preparing black silicon, the spot scan efficiency comparing femtosecond laser is faster, but the black silicon efficiency adopting DRIE not mix sulphur without mask etching preparation is higher, and in sheet between uniformity, sheet consistency good.The invention solves the problem that black silicon area is little, working (machining) efficiency is low that femtosecond laser mixes sulphur.Preparing black silicon by nanosecond laser in a vacuum chamber can by passing into the SF of vacuum chamber
6the air pressure size of gas controls the content mixing sulphur impurity of the black silicon of preparation, and the concentration of sulphur is 10
19-10
21/ cm
3, what can form high concentration mixes sulphur n
+type layer, the doped chalcogenide layer n of this high concentration
+the n-layer of mixing phosphorus with crystal silicon forms height and ties (n
+/ n ties), be conducive to transporting of charge carrier in battery, this height knot can realize significantly improving of open circuit voltage in the full spectral region of the sun.
Application is had the sixth of the twelve Earthly Branches to adopt DRIE without mask etching, the mainly utilization F of the black silicon of DRIE etching preparation
-ion pair silicon chip surface carries out the black silicon that physical chemistry etching forms micro-nano structure, and in corrosion process, silicon there will not be molten condition, only have a small amount of sulphion to be adsorbed on silicon chip surface, but sulfur content is extremely low.The diameter of the nano-micro structure etched is 50nm ~ 1000nm, is highly 100nm to 10000nm, spacing 100nm to 1000nm, and the black silicon Main Function formed in the case is as absorbed layer and antireflection layer, increases the absorption to visible ray.At SF
6carry out RIE in atmosphere to be etched with a small amount of sulphion and to mix in black silicon, but very low (≤10 of sulfur content
16/ cm
3), the black Si semiconductor mixing sulphur can not be formed.Meanwhile, because low sulfur content cannot form the doped chalcogenide layer (n of high concentration
+layer), height knot (n can not be obtained
+/ n ties), make transporting of charge carrier in battery slack-off, affect carrier lifetime and battery conversion efficiency.This solar cell can only form opto-electronic conversion to visible ray, can not effectively absorb near infrared light and produce opto-electronic conversion.
Back side employing crystalline silicon diffusion layer of the present invention is combined with nanosecond laser doped chalcogenide layer to be formed just to be tied, and height knot is convenient to carrier transport, improves battery efficiency; Battery structure positive and negative all has PN junction light-absorbing and electricity-generating, and realize two-sided pair of PN junction, tow sides generate electricity simultaneously, improves the conversion efficiency of battery.The back side of battery structure in application is had the sixth of the twelve Earthly Branches to only have crystal silicon micron and black silicon nanometer to absorb antireflection layer, the back side does not have PN junction, fast and effectively the charge carrier that the energy of absorption changes into cannot be collected rapidly, very little to the contribution of increase photogenerated current, thus affect conversion efficiency.
Cell backside positively charged metal pole of the present invention forms mirror field, the near infrared light reflection penetrating silicon chip is made double-edged PN junction energy re-absorption effect near infrared light, is conducive to the increase of photogenerated current, improves the conversion efficiency of battery; Have the sixth of the twelve Earthly Branches the black silicon of the positive and negative of application respectively to absorb a sunlight, absorb number of times few, and the charge carrier that the near infrared energy of back side absorption produces is difficult to be collected fast and effectively, thus affect the conversion efficiency of battery.
The double-edged black crystal silicon of monocrystalline silicon piece of the present invention and crystal silicon form height and tie micro-structural, the surface field that height knot is formed accelerates the motion of charge carrier, effective electronics-hole pair being separated generation, and height knot increases the near infrared energy of absorption 1.1-2.5 μm, reaches broad absorption.
The present invention use on the positive and negative surface of monocrystalline silicon piece two-step method utilize nanosecond laser technology process preparation Can Liu ?crystal silicon, carry out large area production.Two-step method prepares mobility and the life-span that black crystal silicon effectively improves charge carrier, mix the black crystal silicon of sulphur and crystal silicon to form height and tie, height knot formed surperficial field energy effectively by electronics-hole to separation, thus improve the electric current of battery, utilize the energy of the black crystal silicon PN junction of tow sides and back reflection field re-absorption effect visible ray and near infrared band, reach two-sided broad absorption.Well solve conventional crystalline silicon battery absorption solar energy spectral limit narrower, effectively can not convert thereof into the problem of electric current after improving black silion cell absorb photons, reach the object improving solar cell photoelectric conversion efficiency.
The present invention has following beneficial effect:
1, the present invention crystal silicon PN junction surface by nanosecond laser mix sulphur Bei ?crystal silicon with increase absorption near infrared energy, realize broad absorption, improve the conversion efficiency of existing monocrystalline silicon battery.The preparation technology that the present invention relates to is simple, is convenient to large-scale production.
2, the present invention process on the positive and negative surperficial PN junction of monocrystalline silicon piece preparation Can Liu ?crystal silicon technology form height knot, the surface field that height knot is formed rapidly by electronics-hole to separation, increase carrier lifetime, effectively improve the output current of battery.
3, the present invention first makes crystal silicon PN junction at the positive and negative of monocrystalline silicon piece, realize mixing sulphur by nanosecond laser on two sides crystal silicon knot surface again, two sides all absorbs sunlight, front accepts the direct projection of sunlight, the back side absorbs the near infrared spectrum of back positive electrode mirror field reflection, two sides generates electricity, and reaches the object improving cell photoelectric conversion efficiency.
4, technique provided by the invention and large-scale production compatibility, the solar cell produced by the present invention can absorb solar energy in two sides, and light-absorbing wave band extends to near-infrared, effectively increases the absorption to sunlight.The structure of this battery and manufacture craft can effectively reduce costs, and improve the conversion efficiency of battery.
accompanying drawing illustrates:
Fig. 1 structural representation of the present invention.
Fig. 2 is the standby PN junction layer schematic diagram of monocrystalline silicon piece positive and negative diffusion.
Fig. 3 for monocrystalline silicon piece positive and negative PN junction surface the absorption of mixing prepared by sulphur fall into photosphere schematic diagram.
Fig. 4 is the pectinate texture figure of the back side of the present invention positive and negative electrode.
embodiment:
Embodiment 1:
The invention provides structure of a kind of two-sided black crystalline silicon high-efficiency solar cell and preparation method thereof, crystal silicon PN junction is prepared in the positive and negative processing of monocrystalline silicon piece, positive and negative PN junction surface by nanosecond laser mix sulphur Bei ?crystal silicon, near infrared energy is absorbed to increase, reach the absorption increasing solar spectrum scope, and battery tow sides simultaneously stability solar power generation, thus improve the photoelectric conversion efficiency of solar cell.
With reference to accompanying drawing 1; in figure, concrete layer comprises: front double-layer reflection-decreasing film 4, front first negative electrode 5, front absorb sunken photosphere 3, phosphorus n-layer 2 is mixed in front, P<100> type silicon-based substrate 1, reverse side mix phosphorus n-layer 2, reverse side absorbs and falls into photosphere 3, reverse side second negative electrode 8, reverse side positive and negative electrode protective layer 7, reverse side positive electrode 6, and the positive and negative of P-type silicon base substrate 1 is mixed phosphorus n-layer 2 and absorbed with positive and negative the n falling into photosphere 3
+layer combination forms height knot (n
+/ n ties), then form opto-electronic conversion (n with P-type silicon base substrate 1
+/ n)/p structure, form two separately independently batteries at double-sided solar battery positive and negative, it is that crystalline silicon is placed in chemical corrosion liquid corrosion preparation " pyramid " matte that described positive and negative absorbs the preparation falling into photosphere 3, then is positioned over and comprises SF
6utilize nanosecond laser to mix sulphur in the vacuum chamber of atmosphere and form black crystal silicon, laser energy density is selected at crystal silicon melting Near Threshold, LASER Light Source pulse wavelength is 532nm, repetition rate is 10Hz, the energy adopting laser is 10mJ, make silicon face to a 2 μm degree of depth be in molten condition to carry out mixing sulphur and form black crystal silicon, mix sulphur concentration be about 1.0 × 10
21/ cm
3, visible ray is had to the absorptivity of more than 99%, near infrared spectrum within the scope of 1.1 μm-2.5 μm is had to the absorptivity of more than 95%.
The method of the two-sided black crystalline silicon high-efficiency solar cell of preparation provided by the invention, the method comprises the following steps:
Step 1: be that the monocrystalline silicon piece P < 100 > type silicon-based substrate 1 of 400 μm is positioned in strong base solution and carries out anisotropic etch by thickness, the matte characteristic preparing positive and negative is substantially identical, " pyramid " in matte is highly 18 μm, and " pyramid " bottom width is 27 μm.
Positive and negative for P-type silicon base substrate 1 diffusion into the surface is formed PN junction structure by step 2 in diffusion furnace.P-type silicon base substrate 1 is the monocrystalline silicon piece of P type, and resistivity is 2 Ω .cm.Controlling junction depth during diffusion is 2.5 μm, and the concentration that phosphorus is mixed on surface is 8.0 × 10
17/ cm
3.
Step 3: comprising SF
6utilize nanosecond laser to mix sulphur in the vacuum chamber of atmosphere and form black crystal silicon, laser energy density is selected at crystal silicon melting Near Threshold, LASER Light Source pulse wavelength is 532nm, repetition rate is 10Hz, the energy adopting laser is 10mJ, make the silicon between silicon face to the 2 μm degree of depth be in molten condition to carry out mixing sulphur and form black crystal silicon, mix the concentration of sulphur 1.0 × 10
21/ cm
3, the black crystal silicon of silicon chip positive and negative and crystalline silicon form height junction structure.Height knot accelerates the motion of charge carrier, is effectively separated the electronics-hole pair produced, and black crystal silicon layer increases absorption more than 1.1 μm near infrared energy, reaches the absorption increasing solar spectrum scope.
Step 4: pass through PECVD deposit silicon dioxide or silicon nitride passivation at the lower surface of battery.
Step 5: make electric front negative electrode, makes reverse side pectination positive and negative electrode.
Step 6: the process of alloying, is through high temperature sintering, protects under the atmosphere of nitrogen, obtains Ohm contact type electrode.Alloying is carried out under the protection of nitrogen in oxidation furnace, and the annealing temperature of alloy controls at 580 DEG C.
Step 7: at crystal silicon surface vacuum deposit double layer antireflection coating, double layer antireflection coating is made up of zinc sulphide and magnesium fluoride, and the thickness of zinc sulphide is 80nm, and the thickness of magnesium fluoride is 120nm.
The dense phosphorus diffusion of positive and negative negative electrode region, is positioned over crystal silicon in diffusion furnace, spreads.Phosphorus prediffusion temperature is 950 DEG C, and the time is 25min; Diffusion temperature is 1000 DEG C again, and the time is about 2.5h, phosphorus diffusion depth about 2.3 μm, positive and negative surperficial N-type crystal silicon phosphorus impurities concentration 8.0 × 10
17/ cm
3, square resistance is 120 Ω.
The making of described electrode carries out vacuum coating to the positive and negative of battery, and successively prepare titanium film, nickel film, silverskin obtain positive and negative electrode, the thickness 100nm of platinum/titanium metal thin film, nickel metal film thickness is 200nm, the thick 300nm of silver metal film.
Forming the substrate surface deposit zinc sulphide after black silicon microstructure and magnesium fluoride double layer antireflection coating by vacuum vapor deposition method, the thickness of zinc sulphide is at 80nm, and the thickness of magnesium fluoride is 120nm.
Embodiment 2:
The invention provides structure of a kind of two-sided black crystalline silicon high-efficiency solar cell and preparation method thereof, crystal silicon PN junction is prepared in the positive and negative processing of monocrystalline silicon piece, positive and negative PN junction surface by nanosecond laser mix sulphur Bei ?crystal silicon, form the height knot of black crystal silicon crystal silicon, effective electronics-hole pair being separated generation, mix the black crystal silicon of sulphur and absorb near infrared energy, reach the absorption increasing solar spectrum scope, and battery tow sides simultaneously stability solar power generation, thus improve the photoelectric conversion efficiency of solar cell.
Solar battery structure is with reference to accompanying drawing 1, battery preparation flow is in the same manner as in Example 1, the major parameter related in cell manufacturing process has chemical etching crystal silicon surface formation pyramid size, phosphorus doping density and the degree of depth, nanosecond laser ablation to mix sulphur concentration etc., these parameters are different from embodiment 1, and all the other parameters are consistent with embodiment 1.
Described positive and negative absorbs that to fall into photosphere 3 be that crystalline silicon is placed in highly basic chemical corrosion liquid corrosion preparation " pyramid " matte, then is positioned over and comprises SF
6utilize nanosecond laser to mix sulphur in the vacuum chamber of atmosphere and form black crystal silicon, laser energy density is selected at crystal silicon melting Near Threshold, LASER Light Source pulse wavelength is 532nm, repetition rate is 10Hz, the energy adopting laser is 7mJ, make silicon face to a 1.2 μm degree of depth be in molten condition to carry out mixing sulphur and form black crystal silicon, mix the concentration of sulphur 5.0 × 10
20/ cm
3.
Battery preparation flow is in the same manner as in Example 1, in step 1: be that the monocrystalline silicon piece P-type silicon base substrate 1 of 400 μm is positioned in alkaline solution and carries out anisotropic etch by thickness, the matte characteristic preparing positive and negative is substantially identical, " pyramid " in matte is highly 8 μm, and " pyramid " bottom width is 12 μm.
In step 2: in diffusion furnace, positive and negative for P-type silicon base substrate 1 diffusion into the surface is formed PN junction structure, P-type silicon base substrate 1 is the monocrystalline silicon piece of P type, and resistivity is 2 Ω .cm.Diffusion furnace temperature is 920 DEG C, and the time is 25min; Advance temperature to be 1000 DEG C of time: 60min again, junction depth at 1.5 μm, positive and negative area of illumination N-type crystal silicon phosphorus impurities concentration 3.8 × 10
19/ cm
3, square resistance is 80 Ω.
Embodiment 3:
The invention provides structure of a kind of two-sided black crystalline silicon high-efficiency solar cell and preparation method thereof, crystal silicon PN junction is prepared in the positive and negative processing of monocrystalline silicon piece, positive and negative PN junction surface by nanosecond laser mix sulphur Bei ?crystal silicon, form the height knot of black crystal silicon crystal silicon, effective electronics-hole pair being separated generation, mix the black crystal silicon of sulphur and absorb near infrared energy, reach the absorption increasing solar spectrum scope, and battery tow sides simultaneously stability solar power generation, thus improve the photoelectric conversion efficiency of solar cell.
Solar battery structure is with reference to accompanying drawing 1, battery preparation flow is in the same manner as in Example 1, the major parameter related in cell manufacturing process has chemical etching crystal silicon surface to form pyramid size, phosphorus doping density and the degree of depth, nanosecond laser ablation to mix in sulphur concentration etc. and embodiment 1,2 different, and all the other parameters are consistent with embodiment 1.
Described positive and negative absorbs that to fall into photosphere 3 be that crystalline silicon is placed in chemical corrosion liquid corrosion preparation " pyramid " matte, then is positioned over and comprises SF
6utilize nanosecond laser to mix sulphur in the vacuum chamber of atmosphere and form black crystal silicon, laser energy density is selected at crystal silicon melting Near Threshold, LASER Light Source pulse wavelength is 532nm, repetition rate is 10Hz, the energy adopting laser is 4mJ, make silicon face to a 0.6 μm degree of depth be in molten condition to carry out mixing sulphur and form black crystal silicon, mix sulphur concentration be about 5.3 × 10
19/ cm
3.
Battery preparation flow is in the same manner as in Example 1, in step 1: be that the monocrystalline silicon piece P-type silicon base substrate 1 of 400 μm is positioned in alkaline solution and carries out anisotropic etch by thickness, the matte characteristic preparing positive and negative is substantially identical, " pyramid " height in matte is 2 μm, and " pyramid " bottom width is 3 μm.
In step 2: in diffusion furnace, positive and negative for P-type silicon base substrate 1 diffusion into the surface phosphorus impurities is formed PN junction structure.P-type silicon base substrate 1 is the monocrystalline silicon piece of P type, and resistivity is 2 Ω .cm.Diffusion temperature 950 DEG C, diffusion time is 0.8h, and junction depth is 0.8 μm, positive and negative area of illumination N-type crystal silicon phosphorus impurities concentration 9.0 × 10
18/ cm
3, square resistance is 70 Ω.
In step 3: crystalline silicon is placed in chemical corrosion liquid corrosion preparation " pyramid " matte, then is positioned over and comprises SF
6utilize nanosecond laser to mix sulphur in the vacuum chamber of atmosphere and form black crystal silicon, laser energy density is selected at crystal silicon melting Near Threshold, LASER Light Source pulse wavelength is 532nm, repetition rate is 10Hz, the energy adopting laser is 4mJ, make silicon face to a 0.6 μm degree of depth be in molten condition to carry out mixing sulphur and form black crystal silicon, mix the concentration 5.3 × 10 of sulphur
19/ cm
3, mix the degree of depth of sulphur at 0.6 μm, alloying annealing temperature is 580 DEG C.
Claims (6)
1. two-sided black crystalline silicon high-efficiency solar cell, is characterized in that comprising from upper surface to lower surface:
Front double-layer reflection-decreasing film (4), front first negative electrode (5), front absorb and fall into that phosphorus n-layer (2) is mixed in photosphere (3), front, P-type silicon base substrate (1), reverse side mix phosphorus n-layer (2), reverse side absorbs and falls into photosphere (3), reverse side second negative electrode (8), reverse side positive and negative electrode protective layer (7), reverse side positive electrode (6), and the positive and negative of P-type silicon base substrate (1) mixes the n that phosphorus n-layer (2) and positive and negative absorb sunken photosphere (3)
+layer combination forms height and ties n
+/ n ties, then forms opto-electronic conversion (n with P-type silicon base substrate (1)
+/ n)/p structure, form two respective independently batteries at double-sided solar battery positive and negative,
It is that crystalline silicon is placed in chemical corrosion liquid corrosion preparation " pyramid " matte that described positive and negative absorbs the preparation falling into photosphere (3), then is positioned over and comprises SF
6utilize nanosecond laser to mix sulphur in the vacuum chamber of atmosphere and form black crystal silicon, laser energy density is selected at crystal silicon melting Near Threshold, LASER Light Source pulse wavelength is 532nm, repetition rate is 10Hz, the energy adopting laser is 3-10mJ, make silicon face 0.5 μm to 2 μm degree of depth be in molten condition to carry out mixing sulphur and form black crystal silicon, mix the concentration of sulphur 10
19-10
21/ cm
3.
2. solar cell according to claim 1, is characterized in that phosphorus impurities concentration is mixed 10 in the surface that positive and negative mixes phosphorus n-layer (2)
17-10
19/ cm
3.
3. solar cell according to claim 1, it is characterized in that described front double-layer reflection-decreasing film (4) is made up of zinc sulphide and magnesium fluoride, the thickness of zinc sulphide is between 20-100nm, and the thickness of magnesium fluoride is between 50-250nm.
4. solar cell according to claim 1, it is characterized in that first utilizing chemical solution to etch forms " pyramid " suede structure, " pyramid " height is between 1 μm-20 μm, pyramid base length 2 μm-30 μm, then mix phosphorus at crystalline silicon positive and negative and form n-layer (2), recycling nanosecond laser forms the black crystal silicon of positive and negative and absorbs sunken photosphere (3) on " pyramid " matte.
5. solar cell according to claim 1, what it is characterized in that having a gap with reverse side positive electrode (6) two reverse side second negative electrodes (8) that are symmetry axis and reverse side positive electrode (6) becomes interdigitated structure, the pectinate texture of reverse side positive electrode extends the whole battery lower surface of covering, as cell backside mirror field to battery lower surface.
6. solar cell according to claim 1, is characterized in that its preparation method comprises the following steps:
Step 1: be that monocrystalline silicon piece P-type silicon base substrate (1) between 200 μm to 500 μm is positioned in strong base solution and carries out anisotropic etch by thickness, the matte characteristic preparing positive and negative is substantially identical, in matte " pyramid " height between 1 μm-20 μm, pyramid base length 2 μm-30 μm;
Step 2: in diffusion furnace, positive and negative for P-type silicon base substrate (1) diffusion into the surface is formed PN junction structure, the monocrystalline silicon piece that P-type silicon base substrate (1) is P type, resistivity is 1-10 Ω ﹒ cm, temperature 900-1100 DEG C, diffusion time 30min to 3h, controlling phosphorus impurities diffusion depth by control temperature and time during diffusion is between 0.8 μm to 3 μm, and the concentration controlling to mix phosphorus is 10
17-10
19/ cm
3;
Step 3: utilize nanosecond laser comprising SF
6atmosphere in reach and mix sulphur mixing phosphorus n-layer (2) ablated surface, form the black crystal silicon micro-structural of mixing sulphur in crystal silicon positive and negative N-type layer with this, the black crystal silicon of silicon chip positive and negative and crystal silicon are formed just ties micro-structural,
Step 4: pass through PECVD deposit silicon dioxide or silicon nitride passivation at the lower surface of battery;
Step 5: make electric front negative electrode, makes reverse side pectination positive and negative electrode;
Step 6: the process of electrode metal, is through high temperature sintering, protects under the atmosphere of nitrogen, obtains Ohm contact type electrode;
Step 7: the black crystal silicon surface vacuum deposit double layer antireflection coating in front, double layer antireflection coating is made up of zinc sulphide and magnesium fluoride, and the thickness of zinc sulphide is between 20-100nm, and the thickness of magnesium fluoride is between 50-250nm.
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| CN105655419B (en) * | 2016-03-22 | 2017-10-17 | 电子科技大学 | A kind of method for preparing black silicon material |
| CN105826405A (en) * | 2016-05-17 | 2016-08-03 | 常州天合光能有限公司 | Mono-crystalline silicon double-sided solar cell and preparation method thereof |
| CN107146819B (en) * | 2017-06-22 | 2023-05-23 | 南京南大光电工程研究院有限公司 | Novel thin film solar cell |
| CN110391305A (en) * | 2018-04-20 | 2019-10-29 | 君泰创新（北京）科技有限公司 | A kind of method and solar battery of solar battery preparation |
| CN109037366A (en) * | 2018-08-13 | 2018-12-18 | 晶科能源有限公司 | A kind of multi-level solar battery and preparation method and preparation facilities |
| CN111952377A (en) * | 2020-08-24 | 2020-11-17 | 中国科学院半导体研究所 | Perovskite/silicon laminated solar cell with curved surface light trapping structure and manufacturing method thereof |
| CN116505120A (en) * | 2023-06-27 | 2023-07-28 | 深圳市本征方程石墨烯技术股份有限公司 | Regeneration method of graphite electrode slice leftover materials |
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