CN104409564B - N-type nanometer black silicon manufacturing method and solar cell manufacturing method - Google Patents
N-type nanometer black silicon manufacturing method and solar cell manufacturing method Download PDFInfo
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- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 93
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000007797 corrosion Effects 0.000 claims abstract description 30
- 238000005260 corrosion Methods 0.000 claims abstract description 30
- 229910052709 silver Inorganic materials 0.000 claims abstract description 30
- 239000004332 silver Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 84
- 239000010703 silicon Substances 0.000 claims description 84
- 238000005530 etching Methods 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000012937 correction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 2
- 230000003628 erosive effect Effects 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000002310 reflectometry Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 238000005215 recombination Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 231100000289 photo-effect Toxicity 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Weting (AREA)
Abstract
The invention discloses an N-type nanometer black silicon manufacturing method and a solar cell manufacturing method. The N-type nanometer black silicon manufacturing method comprises steps that: (1), silicon chips after cleaning react in mixed solution of KOH and isopropanol for 0.5-2 hours, and the reaction temperature is 60-100 DEG C; and (2), the N-type silicon chips treated in the step (1) are put in a silver nanometer particle solution for 20-30 minutes in a standing mode, after drying, corrosion treatment on the treated N-type silicon chips is carried out to acquire the N-type nanometer black silicon. For manufacturing a solar cell, an N+ layer, a silicon nitride layer and an electrode layer are sequentially formed at the front surface of the manufactured N-type nanometer black silicon, after sintering, the N-type nanometer black silicon solar cell is manufactured. The manufactured N-type nanometer black silicon solar cell has properties of low reflectivity and high carrier service life and has the conversion efficiency 2.2% higher than that of a cell manufactured through a routine method.
Description
Technical field
The present invention relates to field of photovoltaic technology, be specifically related to the preparation method and too of a kind of N-type nano black silicon
The preparation method of sun energy battery.
Background technology
Optical loss is the principal element hindering solar battery efficiency to improve, and reduces solaode light
Learning loss is to improve that one of battery efficiency important and approach effectively.Crystalline silicon mainly uses at silicon chip at present
" pyramid " texture anti-reflection structure is prepared to reduce reflectance in surface, but it is the most anti-at visible light wave range
Rate of penetrating is more than 10%, and the reflection loss of light is the biggest, governs the further of solar battery efficiency
Improve.
The black silicon structure of nanoporous can effectively reduce the anti-reflection structure of reflectance.It can use electrochemistry
Prepared by method and metal auxiliary catalysis.Metal auxiliary catalysis is because preparation technology is relatively simple, to monocrystalline, many
Crystalline substance all possesses good anti-reflective effect, has potential industrial application value, so by increasing
Pay close attention to.
The black silicon structure of nanoporous utilizing metal auxiliary catalysis to prepare on pyramid texture can obtain
Low-down reflectance, but owing to loose structure is added significantly to silicon chip specific surface area, cause carrier multiple
Close very serious, thus cause the short-circuit current ratio of battery relatively low so that battery efficiency is unable to reach commercialization too
The efficiency that sun energy battery is the highest.National Renewable Energy laboratory photovoltaic center Jihun Oh et al.
(Jihun Oh*, Hao-Chih Yuan and Howard M.Branz.An 18.2%-efficient
black-silicon solar cell achieved through control of carrier recombination in
Nanostructures.Nature Nano technology, 2012,7:743-748) by using tetramethylphosphonihydroxide hydroxide
The nanometer light trapping structure prepared is carried out by ammonium (tetramethy lammonium hydroxide, TMAH)
Etching is revised, and effectively reduces specific surface area and the hole density of silicon chip surface, thus has prepared high efficiency
Black silion cell.But TMAH is relatively costly, obstacle is caused for commercial application.Thus seek one
The etching agent being provided simultaneously with good etching effect with low cost becomes the target that everybody explores.
Additionally, the current black silicon structure of most of nanoporous is all to prepare on P-type silicon sheet, and and P-type silicon
Sheet is compared, and the minority carrier lifetime of the N-type silicon chip of same resistivity is higher than P-type silicon sheet, and this is main
With boron doped P-type silicon sheet there being more boron-oxygen relevant to the effect serving complex centre, and N
Type silicon chip is higher than P-type silicon sheet to the tolerance of metallic pollution, and this point is catalyzed for utilizing silver nano-grain
Nano black silicon structure is prepared in corrosion will more have advantage.So, compared with P-type silicon sheet, at N-type silicon
The silicon chip preparing nano-porous structure on sheet will have higher minority carrier life time, and this is for improving the short of battery
Road electric current is by helpful.
Summary of the invention
It is an object of the invention to by preparing nanometer light trapping structure on N-type czochralski silicon sheet surface, simultaneously
Reduce silicon chip surface specific surface area by alkaline etching, reduce Carrier recombination, increase minority carrier life time, thus have
Effect ground improves battery efficiency, is finally prepared according to existing p-type black silicon solar cell production technology by silicon chip
Obtain high efficiency N+NP back junction solar battery.
The preparation method of the black silicon of the present invention, comprises the following steps:
(1) silicon chip after cleaning is made to react 0.5～2h in the mixed solution of KOH and isopropanol, reaction
Temperature is 60～100 DEG C, and silicon chip surface forms pyramid structure of uniform size.
Cleaning method is as follows: make N-type silicon chip be placed in KOH solution cleaning, removes silicon chip surface damage；
Scavenging period is relevant with the concentration of KOH solution, and usually 10～20min.Preferably, described KOH
The concentration of solution was 15～30mt% (mt% represents molar percentage), removed silicon chip surface damage.Enter
Excellently, the concentration of described KOH solution is 20mt%.
Preferably, in the mixed solution of KOH and isopropanol, the mass concentration of KOH is 3%, isopropanol
Volumetric concentration is 7%.
Further preferably, the reaction temperature of described reaction is 80 DEG C, and the corresponding response time is 60min.
(2) N-type silicon chip after step (1) processes is placed in silver nanoparticle solution standing
20min～30min, after drying and carry out corrosion treatmentCorrosion Science and i.e. obtain N-type nano black silicon.
Silicon chip can form layer of oxide layer in atmosphere, and the surface of silicon oxide is hydrophilic, so in solution
Silver nano-grain can form good contacting with silicon chip surface, during standing, silver nano-grain can deposit
At silicon chip surface, using the catalyst as subsequent reactions.
As preferably, in the silver nanoparticle solution of the present invention, the size (particle diameter) of silver nano-grain is
50～100nm, and even size distribution.
The present invention is prepared via a method which that silver nanoparticle solution is actually the aqueous solution of silver nano-grain,
Concentration can need to set according to reality application, and usually 0.02～0.1mol/L, as preferably 0.05mol/L.
Adopt and prepare silver nano-grain with the following method, the most again the silver nano-grain obtained is configured to desired concn
Silver nanoparticle solution.Wherein, the preparation method of silver nano-grain is as follows:
At 35 DEG C, by 37vol%CH2O joins 0.1mol/L AgNO3In solution, use mass concentration
Be 0.75%～3% polyvinylpyrrolidone (PVP) K-30 as surfactant, be subsequently adding
28vol% ammonia promotes reaction, stirs hybrid reaction 30min, is subsequently adding ethanol and is centrifuged four times, obtain
The silver nano-grain of 50～about 100nm.
Silver nano-grain size can be controlled by the amount of regulation polyvinylpyrrolidone PVP K-30, makes
Argent grain size Control is in the range of 50～100nm.Temperature controls at 35 DEG C, because the reducing power of formaldehyde
In close relations with temperature, the highest reaction of temperature is the fastest.Growth temperature is likely to affect the reunion of Ag granule.
In growth of reuniting, the speed of growth of Argent grain is accelerated when temperature raises.In the later stage in interstage,
The surface potential of Ag granule reduces along with the rising of temperature.At low temperatures, due to electrostatic repulsion forces, reunite
Speed is the lowest.Along with the rising of temperature, surface potential reduces, causes weak repulsive force and the high speed of growth.
The N-type silicon chip forming pyramid structure in described step (2) carries out corrosion treatmentCorrosion Science.As preferably,
Corrosion process is specific as follows:
Make the N-type silicon chip after step (2) processes be placed in corrosive liquid and under shading environment, carry out corrosion instead
Should, described etchant solution is HF, H2O2Mixed liquor with deionized water.
As preferably, HF, H in described corrosive liquid2O2It is 1:(4～6 with the volume ratio of deionized water):
(8～12).Further, HF, H in described corrosive liquid2O2It is 1:5:10 with the volume ratio of deionized water.
Corrosion reaction at room temperature can be carried out.Preferably, during the reaction of corrosion reaction a length of 3min～
6min。
Because H2O2See that light easily decomposes, therefore reaction need to be carried out in light-shielding container.The present invention can pass through
Shading reaction vessel is used to hold corrosive liquid, so that corrosion reaction is carried out under shading environment.
Making silicon chip surface can obtain uniform nanoporous shape structure by corrosion, this structure has the strongest
Light trapping effect, i.e. as light trapping structure.
The generally silicon chip after shape corrosion has become as black silicon, for further enhancing sunken photo effect, the most excellent
Choosing, the N-type silicon chip after corrosion removal performs etching correction, and (light trapping structure corroding most formation continues
Continue and perform etching correction).
Corrosion depth in over etching correction, nanoporous light trapping structure can shoal, and aperture increases, silicon chip
The specific surface area on surface reduces, and surface recombination also reduces.
As preferably, etching directly makes the N-type silicon chip after corrosion treatmentCorrosion Science in etching revises solution when revising
Reaction, described etching correction solution is alkaline solution, such as TMAH, NaOH etc., it is also possible to for acidity
Solution, such as H2O2And HNO3Mixed liquor.
Consider from cost and effect, as preferably, described etching revise solution be concentration be 1～5wt%
(wt% represents mass percent), NaOH solution, during reaction a length of 2～4min.Optimally, during etching
The concentration of the NaOH solution used is 2wt%, a length of 3min during reaction.
Silicon chip surface through corrosion reaction has the remnants of silver nano-grain, and these silver nano-grains can affect
Subsequent applications effect, during as the black silicon structure obtained is applied to solaode, is preparing solaode
Time expansion phosphorus during can diffuse into the Carrier recombination center that formed in silicon chip, reduce minority carrier lifetime,
And then affect battery performance.
Alkali concn is too high and time length all can cause reaction acutely, the nanometer light trapping structure easily will prepared
(i.e. light trapping structure) all etches away, and the too low then reflection of concentration slowly, needs the longer response time.
After alkaline etching, silicon chip surface has sodium ion and exists, and needs to remove with hydrochloric acid.After etching is completed
Sodium ion is remained in N-type silicon chip.Therefore, further revised for etching N-type silicon chip is placed in 10vol%
Hydrochloric acid reaction in 2～5min, then clean and dry up and i.e. obtain final nano black silicon.Generally use and go
Ionized water cleans, and uses nitrogen to dry up.
As preferably, described step (2) also include the N-type silicon chip after corrosion is gone residual treatment with
Remove except the silver nano-grain of residual.N-type silicon chip after corrosion is put into 65wt%HNO by the present invention3Molten
Liquid is placed 1min to remove remaining silver nano-grain.
Present invention also offers the preparation method of a kind of N-type black silicon solar cell, first prepare N-type and receive
The black silicon of rice, then the front surface at the N-type nano black silicon prepared sequentially forms N+ layer, silicon nitride layer
And electrode layer, finally i.e. obtain N-type black silicon solar cell being sintered, described N-type nano black
Silicon is prepared by above-mentioned steps (1)～(3).
The present invention carries out gaseous state diffusion according to existing p-type manufacture of solar cells technique and expands phosphorus with front
Surface forms N+ layer, and silicon nitride layer is prepared by PECVD.Electrode layer passes through silk screen print method
Prepare, and this uses full aluminum back of the body silk screen print method.
One aspect of the present invention rests on silicon chip surface by the silver nano-grain that size is controlled, by silver under room temperature
Catalyzed corrosion prepares reflectance low-down nanometer light trapping structure, then falls into light knot having antiradar reflectivity
Reduce surface recombination by alkaline etching on the basis of structure, increase minority carrier lifetime, thus be effectively increased electricity
The short circuit current in pond and open-circuit voltage.Although during this, reflectance can rise, but is still below
5.5%, compared to the reflectance of the anti-reflection structure more than 10% of existing industry, it has been by a relatively large margin
Decline, and battery efficiency to improve 2.2% compared to the battery without alkaline etching.On the other hand, this
Bright employing N-type silicon chip higher to metal impurities tolerance, because the lacking of the N-type silicon chip of same resistivity
Number carrier lifetime is higher than P-type silicon sheet, thus N-type silicon chip is more beneficial for reducing nano black silicon structure table
The impact that face is compound serious and brings.
Not making specified otherwise in the present invention, described N-type silicon chip is N-type czochralski silicon sheet, N-type silicon
Chip size is according to reality, and resistivity is 1～10 Ω cm.
Compared with prior art, this invention has the advantage that
A silver nano-grain that () present invention uses size controlled is catalyzed preparation on N-type czochralski silicon sheet
Nanometer light trapping structure, this structure is to prepare on the basis of silicon chip pyramid structure, and reflectance can drop to 2.4%
Below.This kind of structure is performed etching by the sodium hydroxide solution using low concentration afterwards, falls into light knot by reducing
The corrosion depth of structure and expansion aperture, thus reduce silicon chip surface specific surface area so that surface recombination reduces,
Minority carrier increases, although etches revised silicon chip reflectance and also can rise accordingly, but is still below
5.5%.The conversion efficiency of this kind of battery is compared conventional method and is wanted high by 2.2%；
B () processing technology of the present invention processing procedure is simple, quick, preparation technology and P-type silicon solar-electricity
The preparation method in pond is compatible, it is not necessary to adding any main equipment, the cost of raw material related to is relatively low, and
And can realize with existing industrial manufacture process compatible with, after process, the surface reflectivity of silicon chip is low, few
The sub-life-span is higher, and battery efficiency can reach 17.8%.
Accompanying drawing explanation
Fig. 1 is the SEM figure on the N-type silicon chip surface corroding 0min in embodiment 1；
Fig. 2 is the SEM figure on the N-type silicon chip surface corroding 4min in embodiment 1；
Fig. 3 be embodiment 1 corrodes 3,4,5,6min time the reflectance map of silicon chip；
Fig. 4 is the N-type silicon chip table that in embodiment 1, corrosion 0min and 4min and embodiment 2 obtain
Reflectance map.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The preparation method of the N-type nano black silicon of the present embodiment comprises the steps:
(1) by soluble in water for 1.5g polyvinylpyrrolidone (PVP K-30), 50g base fluid, base are formed
In liquid, the mass concentration of formaldehyde is 0.74%, and in base fluid, the mass concentration of polyvinylpyrrolidone is 3%, to
Dripping silver nitrate aqueous solution mass concentration in base fluid is 1.7%, and (mass fraction is 28% to be rapidly injected ammonia
Solution 0.6ml), at 35 DEG C react 30min, obtain the solution of silver nano-grain, be subsequently adding ethanol
Centrifugal four times, obtaining silver nano-grain, silver nano-grain is spherical, and silver nano-grain size (particle diameter) is
50nm～100nm.
(2) N-type silicon chip (the primary silicon chip of N-type pulling of crystals) of a size of 156mm × 156mm is thrown
Enter in 20mt%KOH solution, under the conditions of 80 DEG C, react 2min, remove damaged layer on surface of silicon slice.
(3) silicon chip after cleaning is put in the mixed solution of KOH and isopropanol, the wherein matter of KOH
Amount concentration is 3%, and the volumetric concentration of isopropanol is 7%, reacts 60min, at silicon chip under the conditions of 80 DEG C
Surface forms pyramid structure of uniform size.
(4) silicon chip with pyramid structure of step (3) is put into silver nanoparticle solution stand
20min, then dries, the surface texture of the N-type silicon chip obtained such as Fig. 1.
The minority carrier life time being obtained now N-type silicon chip by minority carrier lifetime tester test is 10.18 μ s.Enter one
Step carries out reflectance test, and the reflectance obtained is as shown in curve a in Fig. 4, and reflectance is 13.4%.
(5) silicon chip of step (4) is put into equipped with in the shading reaction vessel of corrosive liquid, at room temperature divide
Do not react 3,4,5,6min, corrosive liquid is HF, H2O2With the mixed liquor of deionized water, solution ratio
For 1:5:10 (volume ratio), form nanometer light trapping structure on pyramid surface, i.e. obtain low surface reflectivity
Monocrystalline silicon solar battery suede, namely N-type nano black silicon.
Fig. 2 is scanning electron microscope (SEM) figure of silicon chip surface after corrosion 4min.Contrast from Fig. 2
Fig. 1 is visible, and after catalyzed corrosion 4min, loose structure uniform fold is received in N-type silicon chip surface, formation
Rice light trapping structure.
Fig. 3 is the reflectance collection of illustrative plates of the silicon chip under the different catalyzed corrosion time, it is seen that at 300～1100nm ripples
Average reflectance in the range of length is reduced to less than 2.4%.Wherein corrode 3,4,5, corresponding anti-of 6min
The rate of penetrating is respectively 2.2%, 1.9%, 2.0% and 2.3%.
Obtain corroding the minority carrier life time of the N-type nano black silicon that 4min obtains through minority carrier lifetime tester test
2.73μs。
(6) silicon chip of step (5) is put into placement 1min in 65wt%HNO3 solution, removes remnants
Silver nano-grain.
The present embodiment carries out gaseous state diffusion expansion phosphorus according further to existing p-type manufacture of solar cells technique exist
Front surface forms N+ layer, PECVD plating silicon nitride, silk screen printing and sintering.But silk screen printing to use entirely
Aluminum back of the body printing.
The solaode obtained in the present embodiment is nano black silicon N+NP solaode.At AM 1.5
Under light intensity, utilize every electric property of cell piece efficiency separator test battery, test result such as table 1
Shown in.Wherein, Voc is open-circuit voltage, and Isc is short circuit current, and FF is fill factor, curve factor, and η is conversion effect
Rate, τ is the minority carrier life time of silicon chip after making herbs into wool.
For ease of contrast, table 1 also list existing N+NP solaode (i.e. prior art) and exist
Electric property under AM 1.5 light intensity and minority carrier life time.Existing N+NP solaode refers to that surface does not has
Have preparation nanometer light trapping structure and only pyramid structure N+NP solaode (be corrosion 0min
In N-type silicon chip).
Table 1
Embodiment 2
Same as in Example 1, except that etch period is 4min in step (5), and in step (6)
With the N-type silicon chip after processing step (5) also by following process between step (7) performs etching and repaiies
Just:
N-type silicon chip after step (6) being processed puts into reaction 3min in 2wt%NaOH solution, with right
The nanometer light trapping structure obtained in step (5) performs etching correction.The most again silicon chip is put into 10vol%'s
In hydrochloric acid, 2min is to remove sodium ion, then uses deionized water cleaning silicon chip, then dries up with nitrogen.
The nano black silicon N+NP solar cell prepared by the present embodiment 2 utilizes battery under AM 1.5 light intensity
Every electric property of sheet efficiency separator test battery, result is as shown in table 1.
The life-span of few son of the N-type nano black silicon that the present embodiment prepares is 5.19 μ s, corresponding reflection
Rate is as shown in curve c in Fig. 4, and reflectance is 5.4%.For ease of comparing, Fig. 4 gives enforcement
Example 1 is corroded the reflectance curve of the N-type silicon chip of 4min, as shown in curve b.
The test parameter of the various embodiments described above is compared discovery, although etch revised silicon chip reflectance and also can
Corresponding rising, but it is still below 5.5%, and the conversion efficiency ratio of solaode is implemented after over etching correction
The conversion efficiency only corroding solaode corresponding for 4min in example is high by 2.2%.
Technical scheme and beneficial effect have been carried out specifically by above-described detailed description of the invention
Bright, it should be understood that to the foregoing is only presently most preferred embodiment of the invention, it is not limited to the present invention,
All made in the spirit of the present invention any amendment, supplement and equivalent etc., should be included in this
Within the protection domain of invention.
Claims (8)
1. the preparation method of a solaode, it is characterised in that preparation N-type nano black silicon, then
It is laggard that front surface at the N-type nano black silicon prepared sequentially forms N+ layer, silicon nitride layer and electrode layer
Row sintering i.e. obtains N-type nano black silicon solar cell；Described electrode layer uses full aluminum back of the body printing legal system
For obtaining；
The preparation method of N-type nano black silicon, comprises the following steps:
(1) N-type silicon chip after cleaning is made to react 0.5～2h in the mixed solution of KOH and isopropanol,
Reaction temperature is 60～100 DEG C；
(2) N-type silicon chip after step (1) processes is placed in silver nanoparticle solution standing
20min～30min, after drying and carry out corrosion treatmentCorrosion Science and i.e. obtain N-type nano black silicon.
2. the preparation method of solaode as claimed in claim 1, it is characterised in that described step
(2) also include in the N-type silicon chip after corrosion treatmentCorrosion Science is performed etching correction.
3. the preparation method of solaode as claimed in claim 2, it is characterised in that etching is revised
Time make the N-type silicon chip after corrosion treatmentCorrosion Science react in etching revises solution.
4. the preparation method of solaode as claimed in claim 3, it is characterised in that described quarter
Erosion revise solution be concentration be the NaOH solution of 1～5wt%.
5. the preparation method of solaode as claimed in claim 4, it is characterised in that etching is revised
Time reaction time a length of 2～4min.
6. the preparation method of the solaode as described in any one claim in claim 2～5,
It is characterized in that, etching also include the N-type silicon chip after corrosion treatmentCorrosion Science is gone before revising residual treatment with
Remove except the silver nano-grain of residual.
7. the preparation method of solaode as claimed in claim 6, it is characterised in that described step
(2) N-type silicon chip after drying is made to react 3min～6min in corrosive liquid to complete corrosion treatmentCorrosion Science in,
Described corrosive liquid is HF, H2O2Mixed liquor with deionized water.
8. the preparation method of solaode as claimed in claim 7, it is characterised in that described corrosion
HF, H in liquid2O2It is 1:(4～6 with the volume ratio of deionized water): (8～12).
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