CN106067488B - A kind of preparation method of the suede structure of crystal silicon solar energy battery - Google Patents
A kind of preparation method of the suede structure of crystal silicon solar energy battery Download PDFInfo
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- CN106067488B CN106067488B CN201610675488.7A CN201610675488A CN106067488B CN 106067488 B CN106067488 B CN 106067488B CN 201610675488 A CN201610675488 A CN 201610675488A CN 106067488 B CN106067488 B CN 106067488B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 100
- 239000010703 silicon Substances 0.000 title claims abstract description 100
- 239000013078 crystal Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims abstract description 48
- 238000005260 corrosion Methods 0.000 claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 25
- 239000012530 fluid Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002310 reflectometry Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000013528 metallic particle Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 229910021418 black silicon Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of preparation method of the suede structure of crystal silicon solar energy battery, comprise the following steps：(1) silicon chip is put into the solution containing metal ion and soaked, silicon chip surface is coated layer of metal nano particle；(2) the metal nanoparticle formation cluster that silicon chip surface is coated is made；(3) with the first chemical corrosion liquid corrosion of silicon surface, porous layer structure is formed；It can obtain the suede structure of crystal silicon solar energy battery.The present invention makes metal nanoparticle formation cluster by the heating of newly-increased step (2), and adjusts the shapes and sizes of metal nanoparticle cluster by adjusting heating-up temperature and duration, is conducive to the control of nano-micro structure pattern.
Description
Technical field
The present invention relates to a kind of preparation method of the suede structure of crystal silicon solar energy battery, belong to solar battery technology
Field.
Background technology
With the extensive use of solar cell module, photovoltaic generation increasingly occupies important proportion in new energy, obtains
Obtained and developed rapidly.In current commercialized solar cell product, crystalline silicon（Monocrystalline and polycrystalline）The market share of solar cell
Maximum, be always maintained at more than 85% occupation rate of market.
At present, in the production technology of solar cell, the suede structure of silicon chip surface can be effectively reduced solar cell
Surface reflectivity, be to influence one of key factor of photoelectric conversion efficiency of the solar battery.In order in crystal silicon solar energy battery
The suede structure that surface has been obtained, to reach preferable anti-reflective effect, people have attempted many methods, and conventional includes machinery
Groove engraving, laser ablation method, reactive ion etching method（RIE）, chemical corrosion method（That is wet etching）Deng.Wherein, mechanical carving groove
Method can obtain relatively low surface reflectivity, but this method causes the mechanical damage of silicon chip surface than more serious, Er Qieqi
Yield rate is relatively low, so in the industrial production using less.It is that different cuttings are made of laser for laser ablation method
The surface of style, striated and inverted pyramid shape all is produced out, and its reflectivity can be with as little as 8.3%, but by it
The efficiency of obtained battery is all than relatively low, it is impossible to be efficiently used for production.RIE methods can be carved using different masterplates
Erosion, etching is usually dry etching, so-called black silicon structure can be formed in silicon chip surface, its reflectivity can be as little as
7.9%, it might even be possible to reach 4%, but be due to that equipment is expensive, production cost is higher, thus industry into production using less.And
The features such as chemical corrosion method has simple technique, cheap price and excellent quality and good compatible existing process, becomes in existing industry using most
Many methods.
At present, it is general in micron order using the suede structure of the crystal silicon solar energy battery of wet etching.Current routine
Way is still further to reduce its surface reflectivity.Application for a patent for invention WO2014120830 (A1) discloses a kind of crystalline silicon and received
The preparation method of rice matte, realizes the control of nanometer suede pattern by way of annealing, but this method complex process, no
The need for industrialized production.In addition, have also appeared the method for corrosion by metal ion, such as Chinese patent in the prior art
CN101573801B, specifically includes following steps：(1) silicon chip is put into the hydrofluoric acid solution containing oxidant and metal salt
In, form porous layer structure；(2) and then with the first chemical corrosion liquid surface etch is carried out；First chemical corrosion liquid is
The mixed solution of hydrofluoric acid and nitric acid；(3) and then above-mentioned silicon chip is put into the second chemical corrosion liquid and impregnated, form matte
Structure；Second chemical corrosion liquid is alkali lye.Wherein, step (1) can also be divided into 2 steps, i.e., first silicon chip is put into containing gold
Belong in the solution of ion and soaking, silicon chip surface is coated layer of metal nano particle, chemical corrosion liquid corrosion of silicon is then used again
Surface, forms porous layer structure.
However, being found in practical application, there are the following problems for the above method：When the concentration of the metal ion in solution is relatively low
When, the metal nanoparticle size of attachment is uneven, and the density variation of diverse location attachment is also larger, so as to cause the nanometer prepared
Micro-structural size is uneven, is open totally different, ultimately results in relatively low electrical property.
Therefore, a kind of preparation method of the suede structure of new crystal silicon solar energy battery is developed, to ensure suede structure
Stability and uniformity and further improve cell piece electricity conversion, it is clear that with positive realistic meaning.
The content of the invention
The goal of the invention of the present invention is to provide a kind of preparation method of the suede structure of crystal silicon solar energy battery.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of matte of crystal silicon solar energy battery
The preparation method of structure, comprises the following steps：
(1) silicon chip is put into the solution containing metal ion and soaked, silicon chip surface is coated layer of metal nanometer
Grain；
(2) the metal nanoparticle formation cluster that silicon chip surface is coated in above-mentioned steps (1) is made；
(3) with the first chemical corrosion liquid corrosion of silicon surface, porous layer structure is formed；
First chemical corrosion liquid is HF and the mixed solution of oxidant；It can obtain the suede of crystal silicon solar energy battery
Face structure.
Above, metal nanoparticle cluster refers to that metal nanoparticle reunites change greatly in the step (2)；Normal conditions
Under, the metal nanoparticle size used is 100 below nm, and 50 ~ 500nm metal nanoparticle is formed after reunion.
In above-mentioned technical proposal, the solution in step (1) is heated, the metal nanoparticle for coating silicon chip surface
Form cluster；
Or, the silicon chip that the surface in step (1) is coated with into metal nanoparticle is placed in inert gas atmosphere and heated
Make the metal nanoparticle formation cluster that silicon chip surface is coated.
The step (2) includes 2 kinds of methods arranged side by side, and one is to directly heat the solution containing metal ion, makes solution temperature
Degree is maintained at 50 ~ 1000 DEG C, and continues 5 ~ 500 seconds；It is preferred that, solution temperature is maintained at 500 ~ 800 DEG C, and continue 10 ~ 100
Second；It is furthermore preferred that making solution temperature be maintained at 550 ~ 650 DEG C, and continue 25 ~ 60 seconds.Second method is to directly heat silicon chip,
Silicon chip is placed in inert gas atmosphere and heated 5 ~ 500 seconds, the temperature of inert gas atmosphere is 50 ~ 1000 DEG C；It is preferred that
, the temperature of inert gas atmosphere is maintained at 200 ~ 500 DEG C, and continue 10 ~ 100 seconds；It is furthermore preferred that making inert gas atmosphere
Temperature be maintained at 250 ~ 350 DEG C, and continue 25 ~ 60 seconds.The inert gas atmosphere can be argon gas atmosphere, helium atmosphere etc.
Deng.
It is preferred that, in the step (2), solution temperature is maintained at 50 ~ 1000 DEG C using the heating means of oil bath.Also may be used
Directly to set the firing equipments such as heating wire in the solution containing metal ion, the solution is directly heated.It is preferred that, the step
Suddenly in (2), the temperature of inert gas atmosphere is made to reach 50 ~ 1000 DEG C using infrared heating method.Certainly, heated inert gas gas
The method of atmosphere has a lot, except above-mentioned infrared heating method, can also be using electrically heated method etc..
Above, the metal ion can be selected from the metal ion of prior art, such as and one in gold, silver, copper, nickel
Plant or several.
Above, the porous layer structure includes Porous Silicon structures, nano thread structure etc..
It is preferred that, HF is also included in the step (1) in the solution containing metal ion.
It is preferred that, in the step (1), the metal ion in solution concentration is less than or equal to 1E-3Mol/L, or, it is molten
Concentration of metal ions is more than 1E in liquid-3HF concentration is less than or equal to 1E while mol/L-2mol/L.This is in order that adjacent
The spacing of two metal nanoparticles is more than 2 times of nanoparticle size.So as to form the micro-structural of above-mentioned similar inverted pyramid.
In above-mentioned technical proposal, in the step (3), in first chemical corrosion liquid, HF concentration is 1 ~ 15 mol/
L, the concentration of oxidant is 0.05 ~ 0.5 mol/L, and corrosion temperature is 25 ~ 90 DEG C, and the time is 1 ~ 10 min.The oxidant can
To be nitric acid, hydrogen peroxide, chromic acid or liquor potassic permanganate.
In above-mentioned technical proposal, after the step (3), also comprise the following steps：
(4) kish particle is removed using the first cleaning fluid；
The one kind of first cleaning fluid in following 4 kinds of solution：Mixed liquor, ammoniacal liquor and the dioxygen of hydrochloric acid and hydrogen peroxide
Mixed liquor, nitric acid, the ammoniacal liquor of water；
The mass concentration of the nitric acid is 5 ~ 69%；The volumetric concentration of the ammoniacal liquor is 1 ~ 30%；
The temperature of first cleaning fluid is 20 ~ 80 DEG C；
(5) and then with the second chemical corrosion liquid surface etch is carried out；
Second chemical corrosion liquid is hydrofluoric acid and nitric acid, and the wherein concentration of hydrofluoric acid is 1 ~ 15 mol/L, nitric acid
Concentration is 0.05 ~ 0.5 mol/L；
Or second chemical corrosion liquid is alkali lye, the alkali lye is selected from sodium hydroxide solution, potassium hydroxide solution, ammonia
Any one or more of water or TMAH；
(6) and then above-mentioned silicon chip is put into the second cleaning fluid and cleaned；
Second cleaning fluid is any one in the mixed liquor of mixed liquor, ammoniacal liquor and the hydrogen peroxide of hydrochloric acid and hydrogen peroxide
Mixed liquor；
(7) and then above-mentioned silicon chip is put into hydrofluoric acid solution and impregnated.
In above-mentioned technical proposal, step（5）Effect be for removing porous surface silicon, step（6）Remove the gold of residual
Belong to particle, step（7）Superficial oxidation silicon layer is removed, actual scheme can be selected according to specific demand.It is preferred that, institute
Step (5), (6), (7) are stated before and after step (7), water-washing step is also equipped with.
The suede structure of the crystal silicon solar energy battery prepared by the above method is claimed in the present invention simultaneously.
The present invention operation principle be：By the heating of newly-increased step (2), make metal nanoparticle formation group
Cluster, and the shapes and sizes of metal nanoparticle cluster are adjusted by adjusting heating-up temperature and duration, be conducive to nanometer
The control of microstructure appearance；Nano-micro structure opening prepared by the present invention is larger（The size of micro-structural of the present invention be 400 ~
800nm, prior art is 200 ~ 300nm), be conducive to the passivation on nano-micro structure surface；In addition, micro-structural prepared by the present invention
It is neat and uniformity is good.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1st, the present invention develops a kind of preparation method of the suede structure of new crystal silicon solar energy battery, passes through what is increased newly
The heating of step (2), makes metal nanoparticle formation cluster, and adjust gold by adjusting heating-up temperature and duration
The shapes and sizes of metal nano-particle cluster, are conducive to the control of nano-micro structure pattern；Experiment is proved：Relative to existing skill
Art, the conversion efficiency of cell piece of the invention can improve 0.20 ~ 0.22% or so, achieve unexpected effect；
2nd, the nano-micro structure opening that prepared by the present invention is larger, and its size is 400 ~ 800 nm, is conducive to nano-micro structure
The passivation on surface；In addition, the micro-structural of the invention prepared is neat and uniformity is good；
3rd, preparation method of the invention is simple and easy to apply, with existing industrialized producing technology compatibility preferably, can quickly move
Plant in industrialized production, suitable for popularization and application.
Brief description of the drawings
Fig. 1 is silicon chip surface depositing metallic nanoparticles and the SEM figures after heating in the embodiment of the present invention one.（Times magnification
Number is 50k）
Fig. 2 is silicon chip surface depositing metallic nanoparticles and the SEM figures after heating in the embodiment of the present invention one.（Times magnification
Number is 30k）
Fig. 3 is the SEM scanning figures of silicon wafer suede in the embodiment of the present invention one.（Multiplication factor is 30k）
Fig. 4 is silicon chip surface depositing metallic nanoparticles and the SEM figures after heating in the embodiment of the present invention two.（Times magnification
Number is 50k）
Fig. 5 is silicon chip surface depositing metallic nanoparticles and the SEM figures after heating in the embodiment of the present invention two.（Times magnification
Number is 30k）
Fig. 6 is the SEM scanning figures of silicon wafer suede in the embodiment of the present invention two.（Multiplication factor is 30k）
Fig. 7 is silicon chip surface depositing metallic nanoparticles and the SEM figures after heating in comparative example one of the present invention.（Times magnification
Number is 50k）
Fig. 8 is silicon chip surface depositing metallic nanoparticles and the SEM figures after heating in comparative example one of the present invention.（Times magnification
Number is 30k）
Fig. 9 is the SEM scanning figures of silicon wafer suede in comparative example one of the present invention.（Multiplication factor is 30k）.
Embodiment
The present invention is further described with reference to embodiment.
Embodiment one：
Referring to shown in Fig. 1 ~ 3, a kind of preparation method of crystal silicon solar energy battery suede structure comprises the following steps：
(1) silicon chip is put into the solution containing metal ion and soaked, silicon chip surface is coated layer of metal nanometer
Grain；
(2) silicon chip that the surface in above-mentioned steps (1) is coated with into metal nanoparticle is placed in inert gas atmosphere and added
Heat treatment 50 seconds, the temperature of inert gas atmosphere is 300 DEG C, the metal nanoparticle formation cluster for coating silicon chip surface；
Here the method for using infrared heating, inert gas atmosphere is argon gas atmosphere；
(3) with the first chemical corrosion liquid corrosion of silicon surface, porous layer structure is formed；Temperature is 590 DEG C, and the time is 2
~10 min；First chemical corrosion liquid is HF and the mixed solution of oxidant；
(4) wash；Then kish particle is removed using the first cleaning fluid；
First cleaning fluid is selected from the mixed liquor of the mixed liquor, ammoniacal liquor and hydrogen peroxide of nitric acid, ammoniacal liquor, hydrochloric acid and hydrogen peroxide
In any one mixed liquor；
(5) wash；Then surface etch is carried out with the second chemical corrosion liquid；Second chemical corrosion liquid is hydrofluoric acid
With the mixed solution of nitric acid；Temperature is 40 DEG C, and the time is 5 ~ 250s；
(6) wash；Then above-mentioned silicon chip is put into the 3rd chemical corrosion liquid and impregnated, form suede structure；It is described
3rd chemical corrosion liquid is alkali lye；
The alkali lye is selected from potassium hydroxide, and the concentration of alkali lye is 0.05 ~ 0.5 mol/L；Dip time is 5 ~ 250s；
(7) wash；Then above-mentioned silicon chip is put into the second cleaning fluid and cleaned, remove the metallic particles of residual；
Second cleaning fluid is the mixed liquor of ammoniacal liquor and hydrogen peroxide；The temperature of the cleaning fluid is 30 DEG C；The ammoniacal liquor
Volumetric concentration be 10%, the volumetric concentration of hydrogen peroxide is 10%；
(8) wash；Then above-mentioned silicon chip is put into hydrofluoric acid solution and impregnated；Washing, you can obtain crystal silicon solar
The suede structure of battery.
Fig. 1 be silicon chip surface depositing metallic nanoparticles and heat after（I.e. after step (2)）SEM figure, its multiplication factor
For 50k；Fig. 2 is also its SEM figures, and its multiplication factor is 30k.Fig. 3 is the SEM scanning figures of silicon wafer suede.
Embodiment two：
Referring to shown in Fig. 4 ~ 6, a kind of preparation method of crystal silicon solar energy battery suede structure comprises the following steps：
(1) silicon chip is put into the solution containing metal ion and soaked, silicon chip surface is coated layer of metal nanometer
Grain；
(2) solution containing metal ion in heating above-mentioned steps (1), makes solution temperature be maintained at 600 DEG C, and hold
Metal nanoparticle formation cluster that is continuous 30 seconds, coating silicon chip surface；
Here can be using the mode of heating for setting heating wire in the solution；
(3) with the first chemical corrosion liquid corrosion of silicon surface, porous layer structure is formed；Temperature is 590 DEG C, and the time is 2
~10 min；First chemical corrosion liquid is HF and the mixed solution of oxidant；
(4) wash；Then kish particle is removed using the first cleaning fluid；
First cleaning fluid is selected from the mixed liquor of the mixed liquor, ammoniacal liquor and hydrogen peroxide of nitric acid, ammoniacal liquor, hydrochloric acid and hydrogen peroxide
In any one mixed liquor；
(5) wash；Then surface etch is carried out with the second chemical corrosion liquid；Second chemical corrosion liquid is hydrofluoric acid
With the mixed solution of nitric acid；Temperature is 40 DEG C, and the time is 5 ~ 250s；
(6) wash；Then above-mentioned silicon chip is put into the 3rd chemical corrosion liquid and impregnated, form suede structure；It is described
3rd chemical corrosion liquid is alkali lye；
The alkali lye is selected from potassium hydroxide, and the concentration of alkali lye is 0.05 ~ 0.5 mol/L；Dip time is 5 ~ 250s；
(7) wash；Then above-mentioned silicon chip is put into the second cleaning fluid and cleaned, remove the metallic particles of residual；
Second cleaning fluid is the mixed liquor of ammoniacal liquor and hydrogen peroxide；The temperature of the cleaning fluid is 30 DEG C；The ammoniacal liquor
Volumetric concentration be 10%, the volumetric concentration of hydrogen peroxide is 10%；
(8) wash；Then above-mentioned silicon chip is put into hydrofluoric acid solution and impregnated；Washing, you can obtain crystal silicon solar
The suede structure of battery.
Fig. 4 be silicon chip surface depositing metallic nanoparticles and heat after（I.e. after step (2)）SEM figure, its multiplication factor
For 50k；Fig. 5 is also its SEM figures, and its multiplication factor is 30k.Fig. 6 is the SEM scanning figures of silicon wafer suede.
Comparative example one：
Referring to shown in Fig. 7 ~ 9, a kind of preparation method of crystal silicon solar energy battery suede structure comprises the following steps：
(1) silicon chip is put into the solution containing metal ion and soaked, silicon chip surface is coated layer of metal nanometer
Grain；
(2) with the first chemical corrosion liquid corrosion of silicon surface, porous layer structure is formed；Temperature is 590 DEG C, and the time is 2
~10 min；First chemical corrosion liquid is HF and the mixed solution of oxidant；
(3) wash；Then kish particle is removed using the first cleaning fluid；
First cleaning fluid is selected from the mixed liquor of the mixed liquor, ammoniacal liquor and hydrogen peroxide of nitric acid, ammoniacal liquor, hydrochloric acid and hydrogen peroxide
In any one mixed liquor；
(4) wash；Then surface etch is carried out with the second chemical corrosion liquid；Second chemical corrosion liquid is hydrofluoric acid
With the mixed solution of nitric acid；Temperature is 40 DEG C, and the time is 5 ~ 250s；
(5) wash；Then above-mentioned silicon chip is put into the 3rd chemical corrosion liquid and impregnated, form suede structure；It is described
3rd chemical corrosion liquid is alkali lye；
The alkali lye is selected from potassium hydroxide, and the concentration of alkali lye is 0.05 ~ 0.5 mol/L；Dip time is 5 ~ 250s；
(6) wash；Then above-mentioned silicon chip is put into the second cleaning fluid and cleaned, remove the metallic particles of residual；
Second cleaning fluid is the mixed liquor of ammoniacal liquor and hydrogen peroxide；The temperature of the cleaning fluid is 30 DEG C；The ammoniacal liquor
Volumetric concentration be 10%, the volumetric concentration of hydrogen peroxide is 10%；
(7) wash；Then above-mentioned silicon chip is put into hydrofluoric acid solution and impregnated；Washing, you can obtain crystal silicon solar
The suede structure of battery.
Fig. 7 be silicon chip surface depositing metallic nanoparticles and heat after（I.e. after step (2)）SEM figure, its multiplication factor
For 50k；Fig. 8 is also its SEM figures, and its multiplication factor is 30k.Fig. 9 is the SEM scanning figures of silicon wafer suede.
Comparison diagram 1,4 and 7, and Fig. 2,5 and 8, it can be seen that after the heating stepses using the present invention, in embodiment
The metal nanoparticle formation cluster of silicon chip surface coating, and cluster does not occur then for comparative example.Compare Fig. 3,6 and 9 again, can be with
Find out, compared with comparative example, micro-structural made from embodiment is bigger, more neat and uniformity is good.
Then, the electrical property of cell piece, testing example and comparative example is made according to prior art, comparing result is as follows：
| Uoc（mV） | Jsc(mA/cm2) | FF(%) | EFF | |
| Comparative example one | 634.8 | 8.931 | 79.79 | 18.59% |
| Embodiment one | 636.8 | 8.979 | 79.97 | 18.79% |
| Embodiment two | 636.8 | 8.982 | 80.03 | 18.81% |
Therefore, relative to comparative example, cell piece Uoc of the invention is obviously improved, and forms what is prepared after cluster
More preferably, conversion efficiency can improve 0.20 ~ 0.22% or so to matte passivation effect, achieve unexpected effect.
Claims (9)
1. a kind of preparation method of the suede structure of crystal silicon solar energy battery, it is characterised in that comprise the following steps：
(1) silicon chip is put into the solution containing metal ion and soaked, silicon chip surface is coated layer of metal nano particle；
(2) the metal nanoparticle formation cluster that silicon chip surface is coated in above-mentioned steps (1) is made；
(3) with the first chemical corrosion liquid corrosion of silicon surface, porous layer structure is formed；
First chemical corrosion liquid is HF and the mixed solution of oxidant, you can obtain the matte knot of crystal silicon solar energy battery
Structure；
The step（2）In, the solution in step (1) is heated, the metal nanoparticle that silicon chip surface is coated is formed
Cluster；Or, the silicon chip that the surface in step (1) is coated with into metal nanoparticle, which is placed in heating in inert gas atmosphere, makes silicon
The metal nanoparticle formation cluster of piece surface coating.
2. the preparation method of the suede structure of crystal silicon solar energy battery according to claim 1, it is characterised in that：It is described
Step（2）In heating-up temperature at 50 ~ 1000 DEG C, and continue 5 ~ 500 seconds.
3. the preparation method of the suede structure of crystal silicon solar energy battery according to claim 1, it is characterised in that：It is described
In step (2), solution temperature is set to be maintained at 50 ~ 1000 DEG C using the heating means of oil bath.
4. the preparation method of the suede structure of crystal silicon solar energy battery according to claim 1, it is characterised in that：It is described
In step (2), the temperature of inert gas atmosphere is set to reach 50 ~ 1000 DEG C using infrared heating method.
5. the preparation method of the suede structure of crystal silicon solar energy battery according to claim 1, it is characterised in that：It is described
HF is also included in step (1) in solution containing metal ion.
6. the preparation method of the suede structure of crystal silicon solar energy battery according to claim 1 or 5, it is characterised in that：
In the step (1), the metal ion in solution concentration is less than or equal to 1E-3Mol/L, or, metal ion in solution concentration
More than 1E-3HF concentration is less than or equal to 1E while mol/L-2 mol/L。
7. the preparation method of the suede structure of crystal silicon solar energy battery according to claim 1, it is characterised in that：It is described
In step (3), in first chemical corrosion liquid, HF concentration is 1 ~ 15 mol/L, and the concentration of oxidant is 0.05 ~ 0.5
Mol/L, corrosion temperature is 25 ~ 90 DEG C, and the time is 1 ~ 10 min.
8. the preparation method of the suede structure of crystal silicon solar energy battery according to claim 1, it is characterised in that：It is described
After step (3), also comprise the following steps：
(4) kish particle is removed using the first cleaning fluid；
The one kind of first cleaning fluid in following 4 kinds of solution：The mixed liquor of hydrochloric acid and hydrogen peroxide, ammoniacal liquor and hydrogen peroxide
Mixed liquor, nitric acid, ammoniacal liquor；
The mass concentration of the nitric acid is 5 ~ 69%；The volumetric concentration of the ammoniacal liquor is 1 ~ 30%；
The temperature of first cleaning fluid is 20 ~ 80 DEG C；
(5) and then with the second chemical corrosion liquid surface etch is carried out；
Second chemical corrosion liquid is hydrofluoric acid and nitric acid, and the wherein concentration of hydrofluoric acid is 1 ~ 15 mol/L, the concentration of nitric acid
For 0.05 ~ 0.5 mol/L；
Or second chemical corrosion liquid be alkali lye, the alkali lye be selected from sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor or
Any one or more of TMAH；
(6) and then above-mentioned silicon chip is put into the second cleaning fluid and cleaned；
Second cleaning fluid is any one mixing in the mixed liquor of mixed liquor, ammoniacal liquor and the hydrogen peroxide of hydrochloric acid and hydrogen peroxide
Liquid；
(7) and then above-mentioned silicon chip is put into hydrofluoric acid solution and impregnated.
9. according to the suede structure of the crystal silicon solar energy battery that any described method is prepared in claim 1 to 8.
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