CN103928542B - A kind of silicon systems solaode and its preparation method and preparation facilitiess and its surface texture - Google Patents
A kind of silicon systems solaode and its preparation method and preparation facilitiess and its surface texture Download PDFInfo
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- CN103928542B CN103928542B CN201410182303.XA CN201410182303A CN103928542B CN 103928542 B CN103928542 B CN 103928542B CN 201410182303 A CN201410182303 A CN 201410182303A CN 103928542 B CN103928542 B CN 103928542B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 239000010703 silicon Substances 0.000 title claims abstract description 210
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 210
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000013528 metallic particle Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 210000004027 cell Anatomy 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000005530 etching Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 97
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 26
- 239000007800 oxidant agent Substances 0.000 claims description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052737 gold Inorganic materials 0.000 claims description 19
- 239000010931 gold Substances 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007921 spray Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 abstract description 2
- 101150054854 POU1F1 gene Proteins 0.000 description 32
- 239000008187 granular material Substances 0.000 description 15
- 239000002105 nanoparticle Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000005507 spraying Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000003595 mist Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 5
- 239000001509 sodium citrate Substances 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 231100000289 photo-effect Toxicity 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 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
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic System
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides the metallic particles that a kind of silicon systems surface structure of solar cell is included in the pit formed in silicon systems solar cell surface and is seated in pit.Also provide using a kind of high silicon systems solaode of quantum efficiency of surface texture of the present invention, and a kind of simple to operate, method that the silicon systems solaode can be prepared with low cost, comprise the steps：Reaction solution is prepared, metallic particles is prepared, etching obtains silicon systems solaode as described in the present invention.A kind of preparation facilitiess of silicon systems solaode are provided also, including for heating the heater of silicon systems solar battery sheet, for reaction solution to be sprayed to the spray equipment on heated silicon systems solar battery sheet, for accommodating the storing apparatus of etching liquid.The present invention is the texture that the pit for being located metallic particles by inside changes silicon systems solar cell surface, produces synergism, and surface plasmon resonance effect is produced when light is irradiated to metallic particles, improves conversion efficiency.
Description
Technical field
The invention belongs to technical field of solar batteries, and in particular to a kind of silicon systems solaode and its preparation method with
Preparation facilitiess and its surface texture.
Background technology
Recently, with research and the development of production technology, solaode will play significant role in traditional energy field.
Mainly there are silicon systems solaode, multi-element compounds thin-film solar cells and organic dye sensitized solar energy in present market
Battery etc..Wherein silicon systems solaode becomes the leading product of solaode because of which in the advantage in terms of raw material deposit
Product, maintain more than 80% market share.Compared with other kinds of solaode, its research and production is relative
Ripe and stable, photoelectric transformation efficiency is higher, and between the coming years, the great demand of world community photovoltaic generation will promote silicon systems
The growth momentum of solaode will keep powerful without taking a turn for the worse.Although silicon systems solaode has many advantages,
But silicon materials price is of a relatively high, this makes which in status in price in more weak tendency.Therefore, in silicon systems solaode
Surface makes light trapping structure, reduces the reflectance on surface, so as to greatly reduce reflection loss of the sunlight in silicon chip surface, has
Help improve the photoelectric transformation efficiency of battery, such that it is able to higher efficiency be obtained using relatively thin silicon materials, effectively can drop
Low cost.Therefore, become current research solaode come the conversion efficiency for improving silicon systems solaode using sunken photo effect
A hot issue.
Now, a kind of effective means for reaching sunken photo effect are exactly to form nanostructured in silicon systems solar cell surface,
Such as nano wire, pit etc., the method for generally adopting is metal auxiliary etch, i.e., existed using the method for chemical deposition or thermal evaporation
Silicon systems solar cell surface forms metallic particles, these metallic particles just as catalyst in the case where chemical reaction is acted on by silicon systems
Solar cell surface is etched into different nanostructureds.But these method operations are comparatively laborious, and relatively costly, this has can
Can affect the future development of silicon systems solaode.
The content of the invention
For the problems of the prior art, the present invention provides a kind of unique structure, the silicon systems solar-electricity of high conversion efficiency
Pool surface structure, and the silicon systems solaode that a kind of quantum efficiency is high, and it is a kind of simple to operate, it is with low cost to prepare
The method and apparatus of the silicon systems solaode.
The present invention is to be achieved through the following technical solutions：
A kind of silicon systems surface structure of solar cell that the present invention is provided, is included in the formation of silicon systems solar cell surface
Pit and the metallic particles being seated in pit.
Preferably, a diameter of 5-100 nanometers of pit, depth are 5-2000 nanometers；Metallic particles is seated in the depth of pit
Spend for 5-2000 nanometers.
Further, a diameter of 20-50 nanometers of pit, depth are 100-1000 nanometers；Metallic particles is seated in pit
Depth is 100-1000 nanometers.
Preferably, metallic particles is gold, silver, copper, aluminum, platinum or palladium.
Preferably, the bottom of pit at least extend into the doping n-layer of silicon systems solaode, the metal in correspondence pit
Grain is seated in doping n-layer.
Preferably, the bottom of pit at least extend into the doping p layers of silicon systems solaode, the metal in correspondence pit
Grain is seated in doping p layers.
Preferably, the bottom of pit at least extend into the p-n junction area of silicon systems solaode, the metal in correspondence pit
Grain is seated in p-n junction area.
The present invention also provides a kind of silicon systems solaode, and its surface texture is using described in one technical scheme of any of the above
Silicon systems surface structure of solar cell.
The present invention also provides a kind of preparation method of silicon systems solaode, comprises the steps：
1) prepare reaction solution：The aqueous solution and one kind of slaine can be generated into gold with aqueous metal salt reaction
Reaction solution is prepared after the go back original reagent solution mixing of metal particles；
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 30-500 DEG C, reaction solution is sprayed to into heating
Silicon systems solar battery sheet on, form corresponding metallic particles on its surface；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet immersion of metallic particles has been formed on surface
In etching liquid, silicon systems solaode as described in the present invention is obtained.
Preferably, metallic particles is gold, silver, copper, aluminum, platinum or palladium；The molar concentration of metal salt solution is:0.001mol/
L-1mol/L, reductant solution molar concentration are 0.0001mol/L-0.1mol/L；Metal salt solution is molten with corresponding reducing agent
The volume ratio of liquid is 1:(1～1000).
Further, etching liquid adopts the mixed solution of aqueous oxidizing agent solution and Fluohydric acid..
Further, aqueous oxidizing agent solution is hydrogen peroxide, Na2S2O8Aqueous solution, KMnO4Aqueous solution, K2Cr2O7Aqueous solution, Fe
(NO3)3Aqueous solution, Ni (NO3)2Aqueous solution, Mg (NO3)2Aqueous solution or nitric acid.
Further, aqueous oxidizing agent solution and the volume ratio of Fluohydric acid. are 1:(1～100), the molar concentration of Fluohydric acid. is
0.01～20mol/L, the molar concentration of oxidant is 0.001～5mol/L.
The present invention also provides a kind of preparation facilitiess of silicon systems solaode, including for heating silicon systems solar battery sheet
Heater, and for reaction solution to be sprayed to the spray equipment on heated silicon systems solar battery sheet, and be used for
Accommodate the storing apparatus of etching liquid.
Preferably, silicon systems solar battery sheet is heated to temperature for 30-500 DEG C by heater.
Compared with prior art, the present invention has following beneficial technique effect：
Silicon systems surface structure of solar cell of the present invention, by forming internal seat in silicon systems solar cell surface
Fall to having the pit of metallic particles so as to which the texture on surface changes, by pit and the metal being seated in pit
Grain produces synergism, and when light is irradiated to the metallic particles being seated in pit, metallic particles can produce surface plasma
Resonance body effect, is embodied in：The effect can excite the free electron of metallic particles to enter silion cell；Local electricity can be produced
It is magnetic field-enhanced, excite more photo-generated carriers in silion cell；Produce the resonance energy in metallic particles and can be transferred to silicon electricity
In pond, more photo-generated carriers are produced.These performances can effectively increase the photo-generated carrier of battery, be conducive to amount of batteries
The raising of sub- efficiency so that the reflectance of silicon systems battery have dropped 8%, and quantum efficiency is obviously improved, short-circuit current density are improved
7%；Considerably increase the efficiency of the silicon systems solaode of this structure.
Further, on the one hand, the diameter control of pit improves sunken light efficiency in nanoscale using its nano effect
Really；The depth of its pits is deeper, and the reflectance of silion cell can be lower such that it is able to better meets the silicon systems under different condition
The requirement of solaode；On the other hand, using the metallic particles being seated in hole realizing surface plasmon resonance effect
Both synergism, can improve the quantum efficiency of solaode.
Further, realize on Different lightwave wave band increasing the specific aim of quantum efficiency by the selection to different metal
By force.
The preparation method of structure of the present invention, by the use of the metallic particles formed on surface as the catalyst of etching,
So that accelerating etching where there is metallic particles on surface, so as to form bowl configurations, knitting for silicon systems solar cell surface is made
State structure changes so as to reduce the reflectance of silicon systems solaode, so as to improve the quantum efficiency of solaode；Gold
Metal particles are collectively forming surface texture with pit, produce synergism, and in illumination, metallic particles produces surface plasma, should
Surface plasma forms exciton or carrier in silicon systems battery, it is also possible to be referred to as electron-hole pair, is conducive to improving silicon
The photovoltaic property of battery.Metallic particles low cost is prepared not only, it is simple to operate；Cost of material is cheap, is readily available, low cost
It is honest and clean, it is adaptable to industrialized production, preparation facilitiess, improve production efficiency can be simplified.
Description of the drawings
Fig. 1 is the schematic cross-section of silicon systems solar cell surface pit in present example 1；Wherein：1 is pit, and 3 are
Silicon systems solar cell surface.
Fig. 2 is the schematic cross-section of silicon systems surface structure of solar cell in present example 1；Wherein：1 is pit, and 2 are
Metallic particles, 3 is silicon systems solar cell surface.
Electron scanning micrographs of the Fig. 3 for the silver nano-grain of silicon systems solar cell surface.
Fig. 4 is the electron scanning micrograph of the silicon systems solaode with surface texture.
Fig. 5 is that the silicon systems solaode with surface texture is reflected in passing through for ultraviolet light to visible ray near infrared light
Spectrogram.
Fig. 6 is the quantum efficiency figure of the silicon systems solaode with surface texture.
Fig. 7 is the preparation facilitiess schematic diagram of the silicon systems solaode with surface texture, wherein：4 heaters, 5 are
Spray equipment, 6 is silicon systems solar battery sheet.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Embodiment 1
A kind of preparation method of silicon systems solaode, comprises the steps：
1) prepare reaction solution：The silver nitrate aqueous solution and one kind of 0.01mol/L can be reacted with silver nitrate aqueous solution
The go back original reagent solution of the 0.007mol/L of silver-colored simple substance granule is generated, with 1:Reaction is prepared after 50 volume ratio mixing molten
Liquid；Using sodium citrate solution as reductant solution in this example.
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 100 DEG C, is utilized including for heating the silicon systems sun
The heater of energy cell piece 6, and the spray equipment 5 on heated silicon systems solar battery sheet is sprayed to for reaction solution,
And for accommodating a kind of preparation facilitiess of silicon systems solaode of the storing apparatus of etching liquid, reaction solution is sprayed to and is added
On the silicon systems solar battery sheet of heat, corresponding Argent grain is formed on its surface；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet for forming Argent grain on surface is immersed in
Volume ratio is 1:Etch in 4 aqueous oxidizing agent solution and the mixed solution of Fluohydric acid., obtain surface texture and be included in the silicon systems sun
The silicon systems solaode of the pit 1 for being formed and the Argent grain being seated in pit 1 on energy battery surface；Wherein, oxidant water
Hydrogen peroxide of the solution using 0.25mol/L, the molar concentration of Fluohydric acid. is 2mol/L.
Resulting silicon systems solaode is purple using Hitachi's S4800 field emission scanning electron microscopes, Lambda950 types
Outer visible infrared spectrometer and quantum efficiency tester are characterized, and the structure on its surface is incorporated shown in Fig. 1 and Fig. 2, utilization
The result of sub- efficiency is calculated short-circuit current density, as a result sees Fig. 3～6.
As depicted in figs. 1 and 2, preparation method of the present invention obtains a kind of silicon systems surface structure of solar cell, including
The pit 1 formed in silicon systems solar cell surface 3 and the metallic particles 2 being seated in pit 1.In this preferred embodiment, silicon
It is solar cell surface 3 in pyramid shape but is not limited only to the structure of pyramid shape, by the process of the preparation method,
Above-mentioned surface texture is formed on pyramid surface, wherein, a diameter of 5-100 nanometers of pit 1, depth are 5-2000 nanometers；
It is 5-2000 nanometers that metallic particles 2 is seated in the depth of pit 1；Diameter of the diameter of metallic particles 2 less than pit 1, metal
Grain 2 in metal be gold, silver, copper, aluminum, platinum or palladium, illustrate by taking silver as an example in this preferred embodiment, it is preferred that pit 1 it is straight
Footpath is 20-50 nanometers, and depth is 100-1000 nanometers；It is 100-1000 nanometers that metallic particles 2 is seated in the depth of pit.
Specifically, as seen from Figure 3, the silver nano-grain that diameter is about 25nm is defined in silicon systems solar cell surface；
From fig. 4, it can be seen that the pit diameter formed on surface is about 30nm, depth is about 200-300nm, and silver nano-grain is located depth about
For 200-300nm；As seen from Figure 5, form the survey of the silicon systems cell piece in 350～1100nm of silicon systems surface structure of solar cell
Under examination optical wavelength, its reflectance reduction 8%；As seen from Figure 6, the silicon systems battery with silicon systems surface structure of solar cell
Quantum efficiency of the piece under the test optical wavelength that wavelength is 350～1100nm strengthens, and tool improves significantly so that short circuit electricity
Current density is also obviously improved, and may be up to 7%.
As shown in Figure 7, it is preferred that a kind of preparation facilitiess of silicon systems solaode, including realize to silicon systems solar-electricity
The heater of the heating of pond piece 6, heater can be integrated with the transmission belt of transmission silicon systems solar battery sheet 6 or mutually independent,
When integrated, heating operation can be when the roller below transmission belt or phase independent heating directly by the silicon systems solar energy after heating
Cell piece 6 is transported to spraying position, and heating-up temperature is 30-500 DEG C；Coordinate spray equipment 4 that reaction solution is sprayed on silicon simultaneously
It is 6 surface of solar battery sheet, as shown in fig. 7, the spraying mouth in spray equipment 4 is located above silicon systems solaode 6, finally
Again the silicon systems solaode 6 of Surface Creation metallic particles 2 is immersed in storing apparatus, by the etching of etching liquid, is being had
Pit 1 is formed where metallic particles 2, pit 1 together constitutes with surface texture with the 1 interior metallic particles 2 being located of pit, had
There is the silicon systems solar battery sheet of surface texture of the present invention.
Embodiment 2
A kind of preparation method of silicon systems solaode, comprises the steps：
1) prepare reaction solution：Can be with tetrachloric acid's gold solution by tetrachloric acid's gold solution and one kind of 0.03mol/L
Reaction generates the go back original reagent solution of the 0.035mol/L of golden simple substance granule, with 1:Prepare after 300 volume ratio mixing anti-
Answer solution；Using sodium citrate solution as reductant solution in this example.
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 200 DEG C, is utilized including for heating the silicon systems sun
The heater of energy cell piece 6, and the spray equipment 5 on heated silicon systems solar battery sheet is sprayed to for reaction solution,
And for accommodating a kind of preparation facilitiess of silicon systems solaode of the storing apparatus of etching liquid, reaction solution is sprayed to and is added
On the silicon systems solar battery sheet of heat, corresponding gold grain is formed on its surface；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet for forming gold grain on surface is immersed in
Volume ratio is 1:Etch in 40 aqueous oxidizing agent solution and the mixed solution of Fluohydric acid., obtain surface texture and be included in the silicon systems sun
The silicon systems solaode of the pit 1 for being formed and the gold grain being seated in pit 1 on energy battery surface；Wherein, oxidant water
Na of the solution using 0.1mol/L2S2O8Aqueous solution, the molar concentration of Fluohydric acid. is 20mol/L.
It is final that the gold nano grain that diameter is about 40nm is defined in silicon systems solar cell surface；On surface, formation is recessed
Hole diameter is about 50nm, and depth is about 700-1000nm, and gold nano grain is located depth and is about 700-1000nm；So that silicon systems are electric
The reflectance in pond have dropped 8%, and quantum efficiency is obviously improved, and short-circuit current density improves 7%.
Embodiment 3
A kind of preparation method of silicon systems solaode, comprises the steps：
1) prepare reaction solution：The copper nitrate aqueous solution and one kind of 0.05mol/L can be reacted with copper nitrate aqueous solution
The go back original reagent solution of the 0.05mol/L of copper simple substance granule is generated, with 1:Reaction solution is prepared after 1 volume ratio mixing；
Using sodium borohydride solution as reductant solution in this example.
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 400 DEG C, is utilized including for heating the silicon systems sun
The heater of energy cell piece 6, and the spray equipment 5 on heated silicon systems solar battery sheet is sprayed to for reaction solution,
And for accommodating a kind of preparation facilitiess of silicon systems solaode of the storing apparatus of etching liquid, reaction solution is sprayed to and is added
On the silicon systems solar battery sheet of heat, corresponding copper granule is formed on its surface；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet for forming copper granule on surface is immersed in
Volume ratio is 1:Etch in 40 aqueous oxidizing agent solution and the mixed solution of Fluohydric acid., obtain surface texture and be included in the silicon systems sun
The silicon systems solaode of the pit 1 for being formed and the copper granule being seated in pit 1 on energy battery surface；Wherein, oxidant water
KMnO of the solution using 0.05mol/L4Aqueous solution, the molar concentration of Fluohydric acid. is 14mol/L.
It is final that the copper nano particles that diameter is about 15nm are defined in silicon systems solar cell surface；On surface, formation is recessed
Hole diameter is about 20nm, and depth is about 5-160nm, and copper nano particles are located depth and are about 5-160nm；So that silicon systems battery is anti-
The rate of penetrating have dropped 8%, and quantum efficiency is obviously improved, and short-circuit current density improves 7%.
Embodiment 4
A kind of preparation method of silicon systems solaode, comprises the steps：
1) prepare reaction solution：The aluminum nitrate aqueous solution and one kind of 0.001mol/L can be reacted with aluminum nitrate aqueous solution
The go back original reagent solution of the 0.0001mol/L of aluminum simple substance granule is generated, with 1:Reaction is prepared after 1000 volume ratio mixing
Solution；Using sodium citrate solution as reductant solution in this example.
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 80 DEG C, is utilized including for heating and conveying silicon
Be the heater of solar battery sheet 6, and the spraying on heated silicon systems solar battery sheet is sprayed to for reaction solution
Device 5, and for accommodating a kind of preparation facilitiess of silicon systems solaode of the storing apparatus of etching liquid, reaction solution is sprayed
Mist forms corresponding alumina particles on its surface on the silicon systems solar battery sheet of heating；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet for forming alumina particles on surface is immersed in
Volume ratio is 1:Etch in 100 aqueous oxidizing agent solution and the mixed solution of Fluohydric acid., obtain surface texture and be included in silicon systems too
The silicon systems solaode of the pit 1 for being formed and the alumina particles being seated in pit 1 on positive energy battery surface；Wherein, oxidant
K of the aqueous solution using 0.25mol/L2Cr2O7Aqueous solution, the molar concentration of Fluohydric acid. is 0.01mol/L.
It is final that the aluminum nanoparticles that diameter is about 30nm are defined in silicon systems solar cell surface；On surface, formation is recessed
Hole diameter is about 50nm, and depth is about 600-900nm, and aluminum nanoparticles are located depth and are about 600-900nm；So that silicon systems battery
Reflectance have dropped 8%, quantum efficiency is obviously improved, and short-circuit current density improves 7%.
Embodiment 5
A kind of preparation method of silicon systems solaode, comprises the steps：
1) prepare reaction solution：By the H of 0.007mol/L2PtCl6Aqueous solution and one kind can be with H2PtCl6Aqueous solution is anti-
The go back original reagent solution of the 0.01mol/L of platinum simple substance granule should be generated, with 1:Reaction is prepared after 100 volume ratio mixing molten
Liquid；Using sodium borohydride solution as reductant solution in this example.
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 500 DEG C, is utilized including for heating and conveying silicon
Be the heater of solar battery sheet 6, and the spraying on heated silicon systems solar battery sheet is sprayed to for reaction solution
Device 5, and for accommodating a kind of preparation facilitiess of silicon systems solaode of the storing apparatus of etching liquid, reaction solution is sprayed
Mist forms corresponding platinum grain on its surface on the silicon systems solar battery sheet of heating；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet for forming platinum grain on surface is immersed in
Volume ratio is 1:Etch in 20 aqueous oxidizing agent solution and the mixed solution of Fluohydric acid., obtain surface texture and be included in the silicon systems sun
The silicon systems solaode of the pit 1 for being formed and the platinum grain being seated in pit 1 on energy battery surface；Wherein, oxidant water
Fe (NO of the solution using 0.0675mol/L3)3Aqueous solution, the molar concentration of Fluohydric acid. is 0.9mol/L.
It is final that the Pt nanoparticle that diameter is about 80nm is defined in silicon systems solar cell surface；On surface, formation is recessed
Hole diameter is about 100nm, and depth is about 100-200nm, and Pt nanoparticle is located depth and is about 100-200nm；So that silicon systems are electric
The reflectance in pond have dropped 8%, and quantum efficiency is obviously improved, and short-circuit current density improves 7%.
Embodiment 6
A kind of preparation method of silicon systems solaode, comprises the steps：
1) prepare reaction solution：By the Ag (NH3) of 1mol/L2+Aqueous solution and one kind can be with Ag (NH3)2+Aqueous solution is anti-
The go back original reagent solution of the 0.1mol/L of silver-colored simple substance granule should be generated, with 1:Reaction is prepared after 900 volume ratio mixing molten
Liquid；Using sodium borohydride solution as reductant solution in this example.
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 300 DEG C, is utilized including for heating and conveying silicon
Be the heater of solar battery sheet 6, and the spraying on heated silicon systems solar battery sheet is sprayed to for reaction solution
Device 5, and for accommodating a kind of preparation facilitiess of silicon systems solaode of the storing apparatus of etching liquid, reaction solution is sprayed
Mist forms corresponding Argent grain on its surface on the silicon systems solar battery sheet of heating；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet for forming Argent grain on surface is immersed in
Volume ratio is 1:Etch in 80 aqueous oxidizing agent solution and the mixed solution of Fluohydric acid., obtain surface texture and be included in the silicon systems sun
The silicon systems solaode of the pit 1 for being formed and the Argent grain being seated in pit 1 on energy battery surface；Wherein, oxidant water
Ni (NO of the solution using 0.1mol/L3)2Aqueous solution, the molar concentration of Fluohydric acid. is 5mol/L.
It is final that the silver nano-grain that diameter is about 35nm is defined in silicon systems solar cell surface；On surface, formation is recessed
Hole diameter is about 50nm, and depth is about 280-400nm, and silver nano-grain is located depth and is about 280-400nm；So that silicon systems battery
Reflectance have dropped 8%, quantum efficiency is obviously improved, and short-circuit current density improves 7%.
Embodiment 7
A kind of preparation method of silicon systems solaode, comprises the steps：
1) prepare reaction solution：Can be anti-with Auric chloride. aqueous solution by the Auric chloride. aqueous solution and one kind of 0.1mol/L
The go back original reagent solution of the 0.08mol/L of golden simple substance granule should be generated, with 1:Reaction is prepared after 400 volume ratio mixing molten
Liquid；Using sodium citrate solution as reductant solution in this example.
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 170 DEG C, is utilized including for heating and conveying silicon
Be the heater of solar battery sheet 6, and the spraying on heated silicon systems solar battery sheet is sprayed to for reaction solution
Device 5, and for accommodating a kind of preparation facilitiess of silicon systems solaode of the storing apparatus of etching liquid, reaction solution is sprayed
Mist forms corresponding gold grain on its surface on the silicon systems solar battery sheet of heating；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet for forming gold grain on surface is immersed in
Volume ratio is 1:Etch in 1 aqueous oxidizing agent solution and the mixed solution of Fluohydric acid., obtain surface texture and be included in the silicon systems sun
The silicon systems solaode of the pit 1 for being formed and the gold grain being seated in pit 1 on energy battery surface；Wherein, oxidant water
Mg (NO of the solution using 0.01mol/L3)2Aqueous solution, the molar concentration of Fluohydric acid. is 1.0mol/L.
It is final that the gold nano grain that diameter is about 50nm is defined in silicon systems solar cell surface；On surface, formation is recessed
Hole diameter is about 60nm, and depth is about 140-320nm, and gold nano grain is located depth and is about 140-320nm；So that silicon systems battery
Reflectance have dropped 8%, quantum efficiency is obviously improved, and short-circuit current density improves 7%.
Embodiment 8
A kind of preparation method of silicon systems solaode, comprises the steps：
1) prepare reaction solution：The aluminum nitrate aqueous solution and one kind of 0.01mol/L can be reacted with aluminum nitrate aqueous solution
The go back original reagent solution of the 0.05mol/L of aluminum simple substance granule is generated, with 1:Reaction is prepared after 200 volume ratio mixing molten
Liquid；Using sodium citrate solution as reductant solution in this example.
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 30 DEG C, is utilized including for heating and conveying silicon
Be the heater of solar battery sheet 6, and the spraying on heated silicon systems solar battery sheet is sprayed to for reaction solution
Device 5, and for accommodating a kind of preparation facilitiess of silicon systems solaode of the storing apparatus of etching liquid, reaction solution is sprayed
Mist forms corresponding alumina particles on its surface on the silicon systems solar battery sheet of heating；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet for forming alumina particles on surface is immersed in
Volume ratio is 1:Etch in 30 aqueous oxidizing agent solution and the mixed solution of Fluohydric acid., obtain surface texture and be included in the silicon systems sun
The silicon systems solaode of the pit 1 for being formed and the alumina particles being seated in pit 1 on energy battery surface；Wherein, oxidant water
Nitric acid of the solution using 5mol/L, the molar concentration of Fluohydric acid. is 10mol/L.
It is final that the aluminum nanoparticles that diameter is about 60nm are defined in silicon systems solar cell surface；On surface, formation is recessed
Hole diameter is about 70nm, and depth is about 300-500nm, and aluminum nanoparticles are located depth and are about 300-500nm；So that silicon systems battery
Reflectance have dropped 8%, quantum efficiency is obviously improved, and short-circuit current density improves 7%.
Embodiment 9
A kind of preparation method of silicon systems solaode, comprises the steps：
1) prepare reaction solution：Can be anti-with chlorine palladium aqueous acid by the chlorine palladium aqueous acid and one kind of 0.0015mol/L
The go back original reagent solution of the 0.009mol/L of palladium simple substance granule should be generated, with 1:Reaction is prepared after 200 volume ratio mixing
Solution；Using sodium borohydride solution as reductant solution in this example.
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 150 DEG C, is utilized including for heating and conveying silicon
Be the heater of solar battery sheet 6, and the spraying on heated silicon systems solar battery sheet is sprayed to for reaction solution
Device 5, and for accommodating a kind of preparation facilitiess of silicon systems solaode of the storing apparatus of etching liquid, reaction solution is sprayed
Mist forms corresponding palladium granule on its surface on the silicon systems solar battery sheet of heating；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet for forming palladium granule on surface is immersed in
Volume ratio is 1:Etch in 60 aqueous oxidizing agent solution and the mixed solution of Fluohydric acid., obtain surface texture and be included in the silicon systems sun
The pit 1 for being formed and the silicon systems solaode for being seated in palladium-silver granule in pit 1 on energy battery surface；Wherein, oxidant water
Hydrogen peroxide of the solution using 2mol/L, the molar concentration of Fluohydric acid. is 11mol/L.
It is final that the palladium nano-particles that diameter is about 3nm are defined in silicon systems solar cell surface；On surface, formation is recessed
Hole diameter is about 5nm, and depth is about 400-630nm, and palladium nano-particles are located depth and are about 400-630nm；So that silicon systems battery
Reflectance have dropped 8%, quantum efficiency is obviously improved, and short-circuit current density improves 7%.
Embodiment 10
On the basis of embodiment 1, metallic particles is made to be seated in doping n-layer；So that the bottom of pit 1 is at least deep into
The doping n-layer of silicon systems solaode, the then metallic particles 2 corresponded in pit 1 can be seated in doping n-layer.
Embodiment 11
On the basis of embodiment 1, metallic particles is made to be seated in doping p layers；So that the bottom of pit 1 is at least deep into
The doping p layers of silicon systems solaode, then correspond to the metallic particles 2 in pit 1 and can be seated in doping p layers.
Embodiment 12
On the basis of embodiment 1, metallic particles is made to be seated in p-n junction area；So that the bottom of pit 1 is at least deep into
The p-n junction area of silicon systems solaode, the then metallic particles 2 corresponded in pit 1 can be seated in p-n junction area.
Other each values not enumerated in a kind of preparation method of silicon systems solaode of the invention, as long as
It is carrying out in its corresponding span and condition needed for meeting reaction, can realizes the purpose of the present invention and reach
The effect of the present invention so that the reflectance of silicon systems battery at least have dropped 8%, and quantum efficiency is obviously improved, short-circuit current density
7% is improve at least, so as to greatly improve the efficiency of silicon systems solaode.
Claims (10)
1. a kind of silicon systems surface structure of solar cell, it is characterised in that by tying in silicon systems solar cell surface (3) pyramid
The pit (1) formed on structure and the metallic particles (2) being seated in pit (1) are formed；The bottom of pit (1) is at least deep into silicon
It is doping n-layer, doping p floor or the p-n junction area of solaode, corresponds to the metallic particles (2) in pit (1) and be seated in doping n
Floor, doping p floor or p-n junction area.
2. a kind of silicon systems surface structure of solar cell according to claim 1, it is characterised in that the diameter of pit (1)
For 5-100 nanometers, depth is 5-2000 nanometers；It is 5-2000 nanometers that metallic particles (2) is seated in the depth of pit (1).
3. a kind of silicon systems surface structure of solar cell according to claim 2, it is characterised in that the diameter of pit (1)
For 20-50 nanometers, depth is 100-1000 nanometers；It is 100-1000 nanometers that metallic particles (2) is seated in the depth of pit (1).
4. a kind of silicon systems surface structure of solar cell according to claim 1 or 2 or 3, it is characterised in that metallic particles
(2) be gold, silver, copper, aluminum, platinum or palladium.
5. a kind of silicon systems solaode, it is characterised in that its surface texture is the silicon as described in claim 1-4 any one
It is surface structure of solar cell.
6. a kind of preparation method of silicon systems solaode, it is characterised in that comprise the steps：
1) prepare reaction solution：The aqueous solution and one kind of slaine can be generated into metal with aqueous metal salt reaction
Reaction solution is prepared after the go back original reagent solution mixing of grain；
2) prepare metallic particles：Silicon systems solar battery sheet is heated to into 100-500 DEG C, reaction solution is sprayed to into the silicon of heating
It is, on solar battery sheet, to form corresponding metallic particles on its surface；
3) etch silicon systems solar battery sheet：The silicon systems solar battery sheet immersion etching of metallic particles has been formed on surface
In liquid, silicon systems solaode as claimed in claim 5 is obtained.
7. the preparation method of a kind of silicon systems solaode according to claim 6, it is characterised in that metallic particles is
Gold, silver, copper, aluminum, platinum or palladium；The molar concentration of metal salt solution is:0.001mol/L-1mol/L, reductant solution mole are dense
Spend for 0.0001mol/L-0.1mol/L；Metal salt solution is 1 with the volume ratio of corresponding reductant solution:(1～1000).
8. a kind of preparation method of silicon systems solaode according to claim 7, it is characterised in that described etching liquid
Using aqueous oxidizing agent solution and the mixed solution of Fluohydric acid..
9. a kind of preparation method of silicon systems solaode according to claim 8, it is characterised in that aqueous oxidizing agent solution
For hydrogen peroxide, Na2S2O8Aqueous solution, KMnO4Aqueous solution, K2Cr2O7Aqueous solution, Fe (NO3)3Aqueous solution, Ni (NO3)2Aqueous solution, Mg
(NO3)2Aqueous solution or nitric acid.
10. a kind of preparation method of silicon systems solaode according to claim 8 or claim 9, it is characterised in that oxidant water
Solution is 1 with the volume ratio of Fluohydric acid.:(1～100), the molar concentration of Fluohydric acid. is 0.01～20mol/L, oxidant mole
Concentration is 0.001～5mol/L.
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| CN107046066A (en) * | 2017-03-09 | 2017-08-15 | 深圳大学 | With suede structure monocrystalline silicon piece and preparation method thereof and silicon solar cell |
| CN107887458A (en) * | 2017-10-11 | 2018-04-06 | 昆明理工大学 | A kind of method that copper catalysis etching silicon prepares morphology controllable matte |
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| CN113512229B (en) * | 2021-07-02 | 2022-10-14 | 中国科学院重庆绿色智能技术研究院 | Micro-nano porous light trapping structure and preparation method thereof |
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| CN102102227A (en) * | 2010-11-18 | 2011-06-22 | 华北电力大学 | Preparation method of hydrophobic light trapping structure on silicon surface |
| CN102332477A (en) * | 2011-07-27 | 2012-01-25 | 常州时创能源科技有限公司 | Light trapping structure for monocrystalline silicon solar cell |
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| CN102553791A (en) * | 2010-12-24 | 2012-07-11 | 无锡尚德太阳能电力有限公司 | Surface treatment method and device for solar cell assembly back plate |
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