CN105140343B - A kind of black silicon structure of polycrystalline and its liquid phase preparation process - Google Patents
A kind of black silicon structure of polycrystalline and its liquid phase preparation process Download PDFInfo
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- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 84
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007791 liquid phase Substances 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 56
- 230000035484 reaction time Effects 0.000 claims description 32
- 229910052709 silver Inorganic materials 0.000 claims description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 25
- 239000004332 silver Substances 0.000 claims description 25
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 14
- 229920005591 polysilicon Polymers 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 38
- 239000010703 silicon Substances 0.000 abstract description 38
- 238000000034 method Methods 0.000 abstract description 30
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000002161 passivation Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 64
- 238000004140 cleaning Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 12
- 238000005530 etching Methods 0.000 description 12
- 238000002310 reflectometry Methods 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 235000009421 Myristica fragrans Nutrition 0.000 description 7
- 230000003667 anti-reflective effect Effects 0.000 description 7
- 239000001115 mace Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000001020 plasma etching Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 235000008216 herbs Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- USWINTIHFQKJTR-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(O)=CC2=C1 USWINTIHFQKJTR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910004042 HAuCl4 Inorganic materials 0.000 description 1
- 229910020776 SixNy Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001039 wet etching 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
-
- 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
-
- 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
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- 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
-
- 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 discloses a kind of black silicon structure of polycrystalline for efficient solar battery and its liquid phase preparation process.Its preparation method includes：(1) prerinse is carried out to silicon chip；(2) using metal assistant chemical corrosion (MACE) technology, black silicon structure is prepared in silicon chip surface；(3) processing is optimized to black silicon structure using NSR (Nano Structure Rebuilding) solution.Eventually form a kind of equally distributed inverted pyramid structure for being easy to passivation.The present invention is a kind of method for optimizing processing to black silicon structure using NSR solution, has huge application potential in prepared by the black silicon solar cell of polycrystalline of high conversion efficiency.
Description
Technical field
The present invention relates to a kind of black silicon structure of polycrystalline and its liquid phase preparation process made for efficient solar battery.
Background technology
In the method for numerous raising solar cell conversion efficiencies, it is a kind of very effective to reduce silicon chip surface reflectivity
Mode.In existing production technology, monocrystalline silicon prepares micron order pyramid structure using alkali making herbs into wool, and polysilicon uses sour making herbs into wool system
Standby micron order vermicular texture, the control of monocrystalline reflectivity is 11% or so, and the control of polycrystalline reflectivity is 24% or so, reflectivity
Still have and more greatly optimize space.Black silicon technology is found in late 1990s, Harvard University Eric professors Mazur etc.
[Applied Physics Letters, 1998,73 (12)：1673-1675] obtained using femtosecond laser technology near ultraviolet
The black silicon absorbed to light (0.25~2.5 μm) almost all of near infrared band.
The preparation technology of black silicon mainly includes femtosecond laser method, reactive ion etching method (RIE), electrochemical erosion method and gold
Belong to auxiliary chemical method (MACE, Metal Assisted Chemical Etching), wherein, femtosecond laser method and RIE it is owned by France in
Dry etching, electrochemical erosion method and MACE are owned by France in wet etching.And these method femtosecond laser method consersion units are expensive, and
Because power density is high in this method, it is easy to which silicon substrate is damaged.Reactive ion etching method, electrochemical erosion method
To belong to metal auxiliary chemical method with industrialized production is best suitable in metal auxiliary chemical method.
Research finds that the anti-reflective effect of the silicon face structure prepared using MACE methods is fabulous.2009, Jilin University
Lu et al. [Langmuir, 2009,25 (14)：7769-7772] Ag assistant chemicals etch is used directly to pyramid silicon face
Corroded, reflectivity of the obtained black silicon sample in visible ray near infrared wavelength region is less than 4%.The same year, the U.S. can
Yuan of Renewable Energy Laboratory (NREL) et al. [Applied Physics Letters, 2009,95 (12)：123501(1-
3) the thick black silicon structures of monocrystalline of 500nm] are prepared for using Au assistant chemical etch, while using the black silicon of the monocrystalline as substrate
It is prepared for solar cell, conversion efficiency 16.8%.In result of study, with the increase of etch period, short wavelength range it is interior
Quantum efficiency reduces, and Yuan is thought caused by being probably highly doped or high surface recombination rate.2011, U.S. NREL's
Fatima Toor et al. [37th IEEE Photovoltaic Specialists Conference, Washington：
IEEE, 2011：1-4] monocrystalline silicon piece for having prepared pyramid structure is placed in HAuCl4, HF and H2O2Mixed solution in carry out
Corrosion is prepared for black silicon structure, and utilizes efficiency of solar cell prepared by the antireflection structure up to 17.1%.The same year, Dalian University of Science ＆ Engineering are big
Liu Aimin et al. [Applied Surface Science, 2011,257：7411-7414] use the conduct of pyramid surface
Substrate, one layer of netted Ag film is deposited thereon using magnetron sputtering method, is then placed in HF and H again2O2Corrode in solution, finally
The black silicon face reflectivity prepared is less than 0.9% (250-1000nm).
The anti-reflective effect that black silicon has had, but the black silicon face out-of-flatness of As-deposited state, and there is larger aspect ratio, that is, increase
Big surface area, typically between 50-150nm, depth can control according to etching time in aperture.Black silicon is reducing surface reflection
While rate, because being provided with bigger specific surface area and introducing the defects of more so that photo-generated carrier is on surface
Compound increase, reduce minority carrier life time (τeff).Current passivation technology, PECVD depositions SixNyFilm can not be passivated black well
Silicon face, turn into the principal element for restricting black silion cell efficiency.2012, U.S. NREL Jihun Oh [Nature
Nanotechnology, 2012,7 (11)：743-748] TMAH (TMAH) solution is used to the black silicon structure of monocrystalline
Expanding treatment has been carried out, while it has been passivated using thermal oxidation method, the black silion cell conversion efficiency of the monocrystalline finally obtained
For 18.2%.Black silicon structure passes through reaming, and structure becomes big, reduces specific surface area, so as to reduce surface recombination.TMAH conducts
The etching agent commonly used in MEMS technology, etching temperature are 80 DEG C, and surface hillock can be formed in etching process, it is smooth to influence surface
Property.The subsequent country has research to carry out expanding treatment to black silicon structure as etching liquid using low concentration NaOH, and revive big Su Xiaodong etc.
People [Advanced Functional Materials, 2014,24：6708-6716] black silicon is carried out using NaOH at 80 DEG C
Reaming, quasi- inverted pyramid structure is obtained, can effectively reduce the Carrier recombination that surface defect is brought.In the paper delivered,
We are [Applied Physics A：Materials Science ＆ Processing, 2014,116 (2)：683-688] adopt
Reaming is carried out to black silicon with normal temperature NaOH, has obtained the black silicon structure in 150-200nm apertures.
In order to obtain the black silicon solar cell of high conversion efficiency, it is effective means to optimize black silicon structure.Whether TMAH or
NaOH solution, ideal structure can be just obtained under high temperature, and structural homogeneity is not so good.Inverted pyramid structure is
Have the excellent structural of antireflective and low specific surface area concurrently, there is the potential quality as efficient black silicon solar cell structure, but need one
The effective and cheap preparation method of kind.The present invention is using NSR (Nano-Structure-Rebuilding) solution to each of silicon
Anisotropy corrosiveness, preparation have the black silicon of inverted pyramid structure.
The content of the invention
Present invention provides a kind of black silicon structure and its liquid phase preparation process for efficient solar battery, it is therefore intended that
While a kind of low cost is provided preparing polycrystalline black silicon, the black silicon of inverted pyramid structure is obtained, to obtain the polycrystalline of high conversion efficiency
Black silion cell.
Therefore, the invention provides following technical scheme：
(1), using standard cleaning PROCESS FOR TREATMENT polysilicon chip.
(2), being immersed in silicon chip surface and one layer of silver nano-grain is deposited in solution one, nano particle size is 50nm or so,
Solution temperature is room temperature.
(3), the silicon chip for having deposited silver nano-grain is immersed in solution two and is corroded (MACE), obtains aperture 50-
100nm, hole depth 500nm nano aperture structure, solution temperature are room temperature.
(4), the black silicon chip corroded is immersed in solution three and cleaned, removes residual silver nano-grain, solution temperature
For room temperature.
(5), the black silicon prepared is immersed in solution four and performed etching, length of side 200nm is prepared, depth 300nm's
The black silicon structure of inverted pyramid.
Described polysilicon chip resistivity 1-3 Ω cm, 200 ± 20 μm of thickness.
Reagent purity used is not less than 99.99% in the technique.
It is 0.001-0.02MAgNO for the composition of solution one in (2) step3+ 0.1-10MHF, the reaction time is in 10-
60s。
It is 0.1-1MH for the composition of solution two in (2) step2O2+ 1-10MHF, the reaction time is in 30-300s.
It is H for the composition of solution three in (3) step2O2∶NH4OH=1: 3, the reaction time is in 180s.
It is NSR solution for solution four in (4) step, consisting of NH4F (40%): H2O2=1: 1-1: 4, concentration is
50%-100%, reaction temperature are 30-60 DEG C, reaction time 60-600s.
The principle of the invention
Because the electronegativity of silicon is 1.90, when the high metallic element of the electronegativity than silicon (Pt, Au, Ag etc.) and silicon contact simultaneously
In HF and H2O2Mixed solution in when, a galvanic cell can be formed in the region of contact, the region that metal contacts with silicon is sun
Pole, and negative electrode is then the high metallic element of electronegativity.
(1) under the catalytic action of noble metal, oxidant (such as H in corrosive liquid2O2) preferentially gone back in precious metal surface
It is former；
(2) hole caused by oxidant is reduced is spread by noble metal and is injected into and noble metal contacts
It is caused to be oxidized to SiO in Si2；
(3) HF along the interface of Si and noble metal by SiO2Remove, the accessory substance of generation is again along Si and noble metal
Interface is diffused into solution；
(4) hole concentration in Si and noble metal interface has the upper limit, therefore, and the Si of noble metal contacts rotten
The speed of erosion is much larger than the corrosion rate without the Si with noble metal contacts；
(5) when the hole-injection rate as Si and the depletion rate in the hole of noble metal interface ratio herein is small, in your gold
The hole of category bottom will be diffused on the region or corrosion hole wall of no noble metal, cause this subregion to be also corroded
Or form micropore silicon structure.
The black silicon structure of polycrystalline of As-deposited state is tiny and coarse, has the shortcomings that high compound for preparing solar cell, therefore
Reaming is carried out using NSR solution.In NSR solution, hydrogen peroxide has anisotropic etch effect, fluorine to silicon chip as oxidant
The concentration of F ion in solution can dynamically be adjusted by changing ammonia, therefore rate of etch is relatively stable.And crystal silicon is due to its anisotropy,
Particularly evident under certain temperature, alkalescence such as NaOH or TMAH solution the anisotropy performance at 80 DEG C are preferable, and in NSR solution
In, 50 DEG C are embodied good anisotropy, and the black silicon of polycrystalline is turned into inverted pyramid structure from nano-pore structure reaming.
Beneficial effect
Compared with existing black silicon technology of preparing, the present invention has the following advantages：
1) cheap MACE preparation technique of liquid phase is used, supports that solution cost is low, can without large-scale high cost vacuum equipment
It is repeated high.
2) new type NS R acid solution counter-boring techniques are used, prepare reflectivity it is low and be easy to passivation inverted pyramid structure,
Structure size is homogeneous, is advantageous to improve black silicon transformation efficiency.
3) temperature is low needed for counter-boring techniques, and needing 80 DEG C without alkaline reagent such as NaOH or TMAH etc. could embody preferably
Anisotropy.
Brief description of the drawings
Fig. 1：The black silicon As-deposited state SEM surface topography maps that embodiment 1 provides.
Fig. 2：Black silicon SEM surface topography maps after the NSR solution reamings that embodiment 1 provides.
Fig. 3：Reflectivity schematic diagram before and after the black silicon reaming that embodiment 1 provides.
Embodiment
In order to control the preparation cost of black silicon, and the conversion efficiency of black silion cell is improved, the embodiments of the invention provide one
The method that kind prepares the black silicon structure of inverted pyramid, including：
(1) cleaning treatment is carried out to silicon chip surface；
(2) silver nano-grain is deposited in silicon chip surface, catalyzed corrosion goes out black silicon nano hole structure；
(2) the black silicon of As-deposited state is subjected to NSR solution cleanings, subtracted so as to form equally distributed inverted pyramid in silicon chip surface
Catoptric arrangement.
In the technical scheme that the embodiment of the present invention is provided, MACE liquid phase methods prepare the uniformity and structure-controllable of black silicon.
Inverted pyramid structure is uniform after carrying out reaming using NSR solution, is advantageous to further battery technique while having reflection preventing ability concurrently,
Specific surface area is small so that compound reduction, is beneficial to the black silicon solar cell for preparing high conversion efficiency.This method cost is relatively low simultaneously,
Technique is simple.And the black silicon of large area can be directly prepared, there is higher production efficiency.
Above is the core concept of the application, below in conjunction with the accompanying drawing in the embodiment of the present invention, to the embodiment of the present invention
In technical scheme be purged, completely describe, it is clear that described embodiment is only part of the embodiment of the present invention,
Rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creative labor
The every other embodiment obtained under the premise of dynamic, belongs to the scope of protection of the invention.
Many details are elaborated in being described below to facilitate a thorough understanding of the present invention, still the present invention can also adopt
It is different from other modes described here with other to implement, those skilled in the art can be in the feelings without prejudice to intension of the present invention
Similar popularization is done under condition, therefore the present invention is not limited by following public specific embodiment.
Embodiment 1：
(1) first acidic oxidation is carried out to polysilicon with the acid hydrogen peroxide containing sulfuric acid to clean, then with the weak base containing amine
Property hydrogen peroxide carry out alkaline oxygenated cleaning, then cleaned with dilute hydrofluoric acid solution, finally with hydrochloric acid mistake
Hydrogen oxide carries out acidic oxidation cleaning, will be rinsed among each cleaning with ultra-pure water (DI water), finally uses low boiling again
Point organic solvent is dried.
(2) immersed in silicon chip surface and one layer of silver nano-grain, 0.002M AgNO are deposited in solution3+ 4M HF, reaction time
50s；
(3) silicon chip for having deposited silver nano-grain is immersed in solution and corroded, 0.3M H2O2+ 1.5M HF are received
Rice pore space structure, the reaction time is in 180s；
(4) the black silicon chip corroded is immersed in solution and cleaned, remove residual silver nano-grain, H2O2： NH4OH=
1: 3, the reaction time is in 180s；
(5) the black silicon prepared is immersed in solution and performed etching, the black silicon structure of inverted pyramid is prepared.Utilize NSR
Solution is acted on the anisotropic etch of silicon, NH4F (40%): H2O2∶H2O=1: 2: 4, reaction temperature is 50 DEG C, the reaction time
300s。
Embodiment result：As shown in figure 1, the black silicon structure of As-deposited state is the nearly 100nm in aperture, hole depth 500nm nano-pore knot
Structure, and many micro-structures are remained on nano-pore structure.As shown in Fig. 2 after NSR and hydrogen peroxide mixed solution reaming,
Black silicon structure turns into inverted pyramid structure, the opening length of side about 200-300nm, depth about 150-250nm, and is evenly distributed.Such as
Shown in Fig. 3, inverted pyramid structure has preferably anti-reflective effect after 50 DEG C of reamings, it is seen that optical band (400-900nm) reflects
Rate is 9.4%, and follow-up because inverted pyramid is easy to be passivated although 4.7% compared to the black silicon of As-deposited state increases
Battery process can be matched more, and the raising for black silion cell efficiency has larger contribution.
Embodiment 2
(1) first carry out acidic oxidation to polysilicon with the acid hydrogen peroxide containing sulfuric acid to clean, with the weak base containing amine
Property hydrogen peroxide carry out alkaline oxygenated cleaning, then cleaned with dilute hydrofluoric acid solution, finally with hydrochloric acid mistake
Hydrogen oxide carries out acidic oxidation cleaning, will be rinsed among each cleaning with ultra-pure water (DI water), finally uses low boiling again
Point organic solvent is dried.
(2) immersed in silicon chip surface and one layer of silver nano-grain, 0.002M AgNO are deposited in solution3+ 4M HF, reaction time
50s；
(3) silicon chip for having deposited silver nano-grain is immersed in solution and corroded, 0.3M H2O2+ 1.5M HF are received
Rice pore space structure, the reaction time is in 180s；
(4) the black silicon chip corroded is immersed in solution and cleaned, remove residual silver nano-grain, H2O2： NH4OH=
1: 3, the reaction time is in 180s；
(5) the black silicon prepared is immersed in solution and performed etching, the black silicon structure of inverted pyramid is prepared.Utilize NSR
Solution is acted on the anisotropic etch of silicon, NH4F (40%): H2O2∶H2O=1: 2: 4, reaction temperature is 50 DEG C, the reaction time
420s。
Embodiment result：Inverted pyramid compares embodiment 1 after increase pore-enlargement, and aperture increases to 500nm, reaming shape
Looks increase with the time and become big.But inverted pyramid structure is similar with monocrystalline silicon micron order pyramid, there is excellent antireflective to imitate
Fruit, it is seen that optical band (400-900nm) reflectivity is 9.9%.
Embodiment 3
(1) first carry out acidic oxidation to polysilicon with the acid hydrogen peroxide containing sulfuric acid to clean, with the weak base containing amine
Property hydrogen peroxide carry out alkaline oxygenated cleaning, then cleaned with dilute hydrofluoric acid solution, finally with hydrochloric acid mistake
Hydrogen oxide carries out acidic oxidation cleaning, will be rinsed among each cleaning with ultra-pure water (DI water), finally uses low boiling again
Point organic solvent is dried.
(2) immersed in silicon chip surface and one layer of silver nano-grain, 0.002M AgNO are deposited in solution3+ 4M HF, reaction time
50s；
(3) silicon chip for having deposited silver nano-grain is immersed in solution and corroded, 0.3M H2O2+ 1.5M HF are received
Rice pore space structure, the reaction time is in 240s；
(4) the black silicon chip corroded is immersed in solution and cleaned, remove residual silver nano-grain, H2O2∶ NH4OH=
1: 3, the reaction time is in 180s；
(5) the black silicon prepared is immersed in solution and performed etching, the black silicon structure of inverted pyramid is prepared.Utilize NSR
Solution is acted on the anisotropic etch of silicon, NH4F (40%): H2O2∶H2O=1: 2: 4, reaction temperature is 50 DEG C, the reaction time
300s。
Embodiment result：After black silicon nano hole deepens, structure is deeper after reaming, compared to the result of embodiment 1, inverted pyramid hole
Footpath approaches, and hole depth is deeper.The reflectivity of visible light wave range (400-900nm) is 9.1%.
Embodiment 4
(1) first carry out acidic oxidation to polysilicon with the acid hydrogen peroxide containing sulfuric acid to clean, with the weak base containing amine
Property hydrogen peroxide carry out alkaline oxygenated cleaning, then cleaned with dilute hydrofluoric acid solution, finally with hydrochloric acid mistake
Hydrogen oxide carries out acidic oxidation cleaning, will be rinsed among each cleaning with ultra-pure water (DI water), finally uses low boiling again
Point organic solvent is dried.
(2) immersed in silicon chip surface and one layer of silver nano-grain, 0.002M AgNO are deposited in solution3+ 4M HF, reaction time
50s；
(3) silicon chip for having deposited silver nano-grain is immersed in solution and corroded, 0.3M H2O2+ 1.5M HF are received
Rice pore space structure, the reaction time is in 30-300s；
(4) the black silicon chip corroded is immersed in solution and cleaned, remove residual silver nano-grain, H2O2∶ NH4OH=
1: 3, the reaction time is in 180s；
(5) the black silicon prepared is immersed in solution and performed etching, the black silicon structure of inverted pyramid is prepared.Utilize NSR
Solution is acted on the anisotropic etch of silicon, NH4F (40%): H2O2∶H2O=1: 2: 4, reaction temperature is 40 DEG C, the reaction time
300s。
Embodiment result：After reducing reaming temperature, reaction rate declines, and anisotropic effect is poor, therefore what is formed falls
Pyramid is relatively irregular.Nevertheless, inverted pyramid structure still has preferably anti-reflective effect (visible ray after 40 DEG C of reamings
The reflectivity of wave band is 9.8%), the raising for black silion cell efficiency has larger contribution.
Embodiment 5
(1) first carry out acidic oxidation to polysilicon with the acid hydrogen peroxide containing sulfuric acid to clean, with the weak base containing amine
Property hydrogen peroxide carry out alkaline oxygenated cleaning, then cleaned with dilute hydrofluoric acid solution, finally with hydrochloric acid mistake
Hydrogen oxide carries out acidic oxidation cleaning, will be rinsed among each cleaning with ultra-pure water (DI water), finally uses low boiling again
Point organic solvent is dried.
(2) immersed in silicon chip surface and one layer of silver nano-grain, 0.02MAgNO are deposited in solution3+ 8M HF, reaction time
50s；
(3) silicon chip for having deposited silver nano-grain is immersed in solution and corroded, 0.8M H2O2+ 6M HF obtain nanometer
Pore space structure, the reaction time is in 240s；
(4) the black silicon chip corroded is immersed in solution and cleaned, remove residual silver nano-grain, H2O2∶ NH4OH=
1: 3, the reaction time is in 180s；
(5) the black silicon prepared is immersed in solution and performed etching, the black silicon structure of inverted pyramid is prepared.Utilize NSR
Solution is acted on the anisotropic etch of silicon, and NH4F (40%): H2O2∶H2O=1: 2: 4, reaction temperature is 50 DEG C, the reaction time
300s。
Embodiment result：After black silicon preparation technology (MACE) changes, cause black silicon structure fine and close and relatively deep, compared to embodiment
1 result, the inverted pyramid aperture formed after reaming diminish, and hole depth is deeper.The reflectivity of visible light wave range (400-900nm) is
8.1%.
Embodiment 6
(1) first carry out acidic oxidation to polysilicon with the acid hydrogen peroxide containing sulfuric acid to clean, with the weak base containing amine
Property hydrogen peroxide carry out alkaline oxygenated cleaning, then cleaned with dilute hydrofluoric acid solution, finally with hydrochloric acid mistake
Hydrogen oxide carries out acidic oxidation cleaning, will be rinsed among each cleaning with ultra-pure water (DI water), finally uses low boiling again
Point organic solvent is dried.
(2) immersed in silicon chip surface and one layer of silver nano-grain, 0.002M AgNO are deposited in solution3+ 4M HF, reaction time
50s；
(3) silicon chip for having deposited silver nano-grain is immersed in solution and corroded, 0.3M H2O2+ 1.5M HF are received
Rice pore space structure, the reaction time in 240s,；
(4) the black silicon chip corroded is immersed in solution and cleaned, remove residual silver nano-grain, H2O2∶ NH4OH=
1: 3, the reaction time is in 180s；
(5) the black silicon prepared is immersed in solution and performed etching, the black silicon structure of inverted pyramid is prepared.Utilize NSR
Solution is acted on the anisotropic etch of silicon, and NH4F (40%): H2O2∶H2O=1: 4: 4, reaction temperature is 50 DEG C, the reaction time
300s。
Embodiment result：Hydrogen peroxide ratio in NSR solution is increased, makes corrasion stronger, compared to the result of embodiment 1,
Close to polishing effect, pyramid structure is etched close to smooth, anti-reflective effect decline silicon chip.
Claims (6)
1. a kind of liquid phase preparation process of the black silicon structure of polycrystalline made for solar cell, it is characterised in that the structure is to pass through
The equally distributed inverted pyramid structure of nanoscale that the reaming of metal assistant chemical etch combination NSR solution obtains, subtracts possessing
It is easy to be passivated while reflecting effect, for preparing the black silicon solar cell of polycrystalline, the preparation method comprises the following steps：
(1), polysilicon chip surface is cleaned, the polysilicon chip surface is immersed one layer of silver nanoparticle is deposited in solution one
Grain, nano particle size are 50nm or so, and solution temperature is room temperature；
(2), the polysilicon chip for having deposited silver nano-grain is immersed in solution two and corroded, obtains aperture 50-100nm, hole
The deep 500nm black silicon chip of nano aperture structural polysilicon, solution temperature is room temperature；
(3), the black silicon chip of the polycrystalline corroded is immersed in solution three and cleaned, removes residual silver nano-grain, solution temperature
For room temperature；
(4), the black silicon chip of the polycrystalline prepared is immersed in NSR solution and corrodes reaming；The composition of NSR solution is 40%NH4F∶H2O2
=1: 1-1: 4, concentration 50%-100%, reaction temperature are 30-60 DEG C, reaction time 60-600s；The length of side is prepared
100-500nm, depth the 100-500nm equally distributed black silicon structure of inverted pyramid polycrystalline.
2. being used for the liquid phase preparation process for the black silicon structure of polycrystalline that solar cell makes according to claim 1, its feature exists
In：Polysilicon chip resistivity described in step (1) is 1-3 Ω cm, and thickness is 200 ± 20 μm.
3. being used for the liquid phase preparation process for the black silicon structure of polycrystalline that solar cell makes according to claim 1, its feature exists
In：The chemical reagent purity of solution used in step (1) to step (4) is not less than 99.99%.
4. being used for the liquid phase preparation process for the black silicon structure of polycrystalline that solar cell makes according to claim 1, its feature exists
In：The chemical reagent composition of solution one is 0.001-0.02M AgNO in step (1)3+ 0.1-10M HF, reaction time 10-
60s。
5. being used for the liquid phase preparation process for the black silicon structure of polycrystalline that solar cell makes according to claim 1, its feature exists
In：The chemical reagent composition of solution two is 0.1-1M H in step (2)2O2+ 1-10M HF, reaction time 30-300s.
6. being used for the liquid phase preparation process for the black silicon structure of polycrystalline that solar cell makes according to claim 1, its feature exists
In：The chemical reagent composition of solution three is H in step (3)2O2∶NH4OH=1: 3, reaction time 180s.
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