CN105428434B - A kind of polysilicon surface inverted pyramid structure and preparation method thereof - Google Patents
A kind of polysilicon surface inverted pyramid structure and preparation method thereof Download PDFInfo
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- CN105428434B CN105428434B CN201610005713.6A CN201610005713A CN105428434B CN 105428434 B CN105428434 B CN 105428434B CN 201610005713 A CN201610005713 A CN 201610005713A CN 105428434 B CN105428434 B CN 105428434B
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 108
- 229920005591 polysilicon Polymers 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 209
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 198
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 95
- 239000010703 silicon Substances 0.000 claims abstract description 95
- 229910021418 black silicon Inorganic materials 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 58
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims abstract description 36
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000007797 corrosion Effects 0.000 claims abstract description 7
- 238000005260 corrosion Methods 0.000 claims abstract description 7
- 229960002050 hydrofluoric acid Drugs 0.000 claims description 106
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 239000011259 mixed solution Substances 0.000 claims description 43
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 42
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 34
- 229910017604 nitric acid Inorganic materials 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 23
- 230000002000 scavenging effect Effects 0.000 claims description 22
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000001020 plasma etching Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910018503 SF6 Inorganic materials 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 4
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 210000001367 artery Anatomy 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000010884 ion-beam technique Methods 0.000 claims 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 claims 1
- 210000003462 vein Anatomy 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 10
- 238000002310 reflectometry Methods 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 5
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000010307 cell transformation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005406 washing 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of polysilicon surface inverted pyramid structure and preparation method thereof, the present invention carries out black silicon making using different methods, then sample is placed in the mixed liquor of hydrogen peroxide and monoethanolamine and embathed, the mixed liquor that washed black silicon is placed in into hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride again is reprocessed, and forms polysilicon surface inverted pyramid structure.Present invention employs a kind of wet chemical method different from acid and alkali corrosion, this method can reduce anisotropic influence to greatest extent, can by the black silicon of different nanostructureds by oxide etch into the nanometer suede structure for having well-regulated inverted pyramid structure.The polysilicon inverted pyramid light trapping structure of the present invention is relative to conventional multi-crystalline silicon matte, its utilization rate to light is higher, reflectivity is lower, because of its inverted pyramid structure feature, relative to the high surface recombination of traditional black small and dense structure of silicon, its surface recombination is substantially reduced so that solar cell it is more efficient.
Description
Technical field
The invention belongs to technical field of solar batteries, more particularly to a kind of polysilicon surface inverted pyramid structure and its system
Preparation Method.
Background technology
Conventional polysilicon suede structure is micron order vermicular texture, the matte of polysilicon make be using silicon it is each to
It is images generated, alveolate texture is formed on surface using acid corrosion, with certain light trapping effect, silicon chip surface can be reduced
Reflectivity.
Now there is a kind of new nanometer light trapping structure to be commonly referred to as black silicon, it passes through appropriate etching or the side of corrosion
The pore space structure of the various circular cones of method nanoscale, the forest structure of cylinder or dense distribution, with good light trapping effect, energy
Enough significantly reduce the reflectivity of silicon chip surface, it is considered to be the structure of solar cell transformation efficiency can be effectively improved.At present
There are many laboratories to prepare black silicon by different methods.Such as femtosecond laser pulse method, plasma etching method and gold
Belong to ion auxiliary etch method etc..Distinct methods can prepare different black silicon structures and reflectivity can be made low.But this
Kind original black silicon nanometer light trapping structure generally has that structure is compared with small, close, depth and defect is more, or even has impurity contamination on surface,
Although optically with the obvious advantage, with current crystal silicon solar battery manufacturing process and mismatching.Black silicon structure if not done by
If optimization, serious surface recombination will be caused on the contrary to decline the efficiency of solar cell.
Polysilicon surface inverted pyramid light trapping structure using a kind of wet chemical method different from acid and alkali corrosion by being made, most
The anisotropic influence of the reduction of limits, can be well-regulated into tool by oxide etch by the black silicon of different nanostructureds
The nanometer suede structure of pyramid structure.Compared with prior art, its advantage is that the structure of the black Si reconstructed surface of polycrystalline is
Inverted pyramid structure and structure is larger, hole is deeper, preferably ensure that the characteristic of black silicon antiradar reflectivity makes silicon chip be easy to passivation again,
So as to improve the electrical property of polycrystalline solar cell, the transformation efficiency of battery is effectively improved.And to the less demanding of equipment,
It can be used widely during industrialization production.
Therefore, the absorption of silicon chip surface light how is increased, while not increasing its surface recombination, it is possible to increase solar cell turns
Change efficiency, and method it is convenient it is feasible can industrialization, it is significant.
The content of the invention
Goal of the invention：It is existing to solve the invention provides a kind of polysilicon surface inverted pyramid structure and preparation method thereof
The problem of having in technology.
Technical scheme：To achieve these goals, the present invention uses following technical scheme：
A kind of preparation method of polysilicon surface inverted pyramid structure, it is characterised in that comprise the following steps：
Step 1: polysilicon damaged layer on surface of silicon slice is removed：By the polysilicon silicon chip after over cleaning be placed in hydrofluoric acid and
HNO3Mixed solution in, carry out surface mechanical damage layer removal；
Step 2: the black silicon structure of polysilicon silicon chip surface makes：Swash using metal ion auxiliary etch method or using femtosecond
Light pulse method or reactive ion etching method carry out black silicon making；
Step 3: the making of polysilicon silicon chip surface inverted pyramid texture：First by the black silicon of the above method be placed in containing
Embathed in the mixed liquor of hydrogen peroxide and monoethanolamine, washed black silicon is then placed in hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride
Mixed liquor embathe again；Or only black silicon is placed in hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride mixed liquor embathe；I.e.
Inverted pyramid structure can be made in polysilicon silicon chip surface；
Step 4: the cleaning of polysilicon silicon chip：Surface had into the polysilicon silicon chip of inverted pyramid structure in HF solution
Cleaning, places into pure water cleaning, finally dries.
Further, hydrofluoric acid and HNO in the step one3Mixed solution in, the volume fraction of hydrofluoric acid is 12%
~15%, HNO3Volume fraction 60%~65%, pure water volume fraction 20%~28%, reaction temperature be 7~9 DEG C, reaction
Time is 1-2min.
Further, metal ion auxiliary etch method in the step 2：The polysilicon silicon chip removed after damage layer is put
Argent grain deposition is carried out in the mixed solution of hydrofluoric acid and silver nitrate, then the polysilicon silicon chip for depositing completion is placed in hydrofluoric acid
With chemical attack is carried out in the mixed solution of hydrogen peroxide, obtain nano black silicon；
Further, in the step 2 metal ion auxiliary etch method, hundred in the mixed solution of hydrofluoric acid and silver nitrate
Point specific concentration proportioning is, pure water 92%-99%, hydrofluoric acid 0.1%~3% and silver nitrate 0.1%~5%, and reaction temperature is 8
DEG C -30 DEG C, the reaction time is 10~100s；Percent concentration proportioning is in the mixed liquor of hydrofluoric acid and hydrogen peroxide, pure water 85%-
98%th, hydrogen peroxide 1%-5% and hydrofluoric acid 1%-10%, reaction temperature is 8 DEG C -60 DEG C, and the reaction time is 120s-500s.
Further, femto-second laser pulse method in the step 2：Black silicon making is carried out with laser pulse method, by polysilicon
Silicon chip formation mask layer, forms predetermined pattern via-hole array on mask layer, graphic mask polysilicon silicon chip is performed etching,
Predetermined pattern groove array is formed on polysilicon silicon chip, mask layer is removed, polysilicon silicon chip is placed in sulfur hexafluoride or hydrogen sulfide
In gas, using the laser of 400-1000 wavelength, its pulse is 500-2100 irradiation silicon chip, obtains nano black silicon；
Further, reactive ion etching method in the step 2：Polysilicon silicon chip is placed in vacuum chamber, with low energy from
Polysilicon silicon chip after irradiation, is then placed in reactive ion etching vacuum chamber by beamlet uniform irradiation polysilicon silicon chip, is made
Black silicon sample；
Further, in the step 3, the mixed liquor containing hydrogen peroxide and monoethanolamine, its percent concentration proportioning is pure
Water 68%-97%, monoethanolamine 0%-2%, ammoniacal liquor 1%~10% and hydrogen peroxide 2%-20%, reaction temperature are 8 DEG C -30 DEG C, instead
It is 60s-500s between seasonable；Hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percent concentration proportioning are pure water
73%-94.9%, hydrogen peroxide 4%-7%, hydrofluoric acid 0.1%-3%, metaphosphoric acid 0%-2% and ammonium fluoride 1%-15%, reaction
Temperature is 50 DEG C -80 DEG C, and the reaction time is 50s-600s.
Further, there is the polysilicon silicon chip of inverted pyramid structure to insert ammoniacal liquor again and double the surface that step 3 is obtained
Cleaned in the mixed liquor of oxygen water, then carry out step 4；The mixed liquor of the ammoniacal liquor and hydrogen peroxide, its percent concentration proportioning is pure
Water 70%~97%, hydrogen peroxide 2%~20% and ammoniacal liquor 1%~10%, reaction temperature be 8 DEG C -30 DEG C, the reaction time be 30~
180s。
Further, HF volume fraction is 1%~5% in the step 4, the volume fraction of pure water for 95%~
99%, scavenging period scope is 40~120s, and pure water scavenging period scope is 40~120s.
A kind of polysilicon surface inverted pyramid structure, polysilicon silicon chip surface has several inverted pyramid structures, each falls
Pyramid structure is shown as square aperture on the surface of polysilicon silicon chip, along four sides of square aperture respectively into polysilicon chip
Portion tilts extension, and four tapered planars connect the taper to form inverted pyramid structure；The side of the square aperture of inverted pyramid structure
A length of 100-1000 nanometers, vertical depth is 50-800 nanometers, its inclined tapered planar normal and polysilicon silicon chip upper surface
Angle between normal is 20-65 degree；On polysilicon silicon chip surface, inverted pyramid structure is random distribution, and each other
There is superposition.
Beneficial effect：Present invention employs a kind of wet chemical method different from acid and alkali corrosion, this method can be with maximum limit
The anisotropic influence of the reduction of degree, can make it have many of rule by the black silicon of different nanostructureds by oxide etch
Crystal silicon inverted pyramid structure；The present invention can be reprocessed to the black silicon that different nanostructureds and any method make, and be formed many
Crystal silicon inverted pyramid structure, polysilicon inverted pyramid structure is relative to conventional multi-crystalline silicon matte, with more excellent sunken light efficiency
Really, the utilization rate to light is higher, and reflectivity is lower, and relative to the high surface recombination of traditional black small and dense structure of silicon, its surface is answered
Closing substantially reduces, and the secondary structure formed on the basis of original polycrystalline structure is larger, i.e. the size of inverted pyramid structure is bigger, golden word
The vertical depth of tower structure is deeper, the present invention preferably ensure that the characteristic of black silicon antiradar reflectivity again so that silicon chip be easy to be passivated,
So as to improve the electrical property of polycrystalline solar cell, the transformation efficiency of solar cell is effectively improved so that solar energy
Battery it is more efficient；Nanostructured falls into light effect significantly, specific yield is carried in true environment close to optical wavelength simultaneously
Rise notable；The inventive method is simple, easy to operate, with low cost, to the less demanding of equipment, the energy during industrialization production
Access extensive use.
Brief description of the drawings
Fig. 1 is polycrystalline surface inverted pyramid structure SEM image in embodiment 1；
Fig. 2 is that black silicon does not reprocess SEM image during the present invention contrasts 1；
Fig. 3 is conventional matte SEM image in present invention contrast 2.
Embodiment
The present invention is further described with reference to embodiment.
A kind of polysilicon surface inverted pyramid structure of the present invention and preparation method thereof, is related to and make on the polysilicon golden word
Tower solar cell makes, to be made of a kind of wet chemical method different from acid and alkali corrosion, reduce to greatest extent it is each to
The influence of the opposite sex, can by the black silicon of different nanostructureds by oxide etch into the nanometer for having well-regulated inverted pyramid structure
Suede structure.
Embodiment 1
A kind of manufacture method of polycrystalline surface inverted pyramid structure texture, comprises the following steps：
Step 1: from p-type polysilicon material, specification is 156cm*156cm, thickness is 200um, and polysilicon silicon chip is put
In hydrofluoric acid and HNO3Mixed solution in corrode, carry out surface mechanical damage layer removal；
Step 2: carrying out black silicon making with metal ion auxiliary etch method method, silicon chip is placed in hydrofluoric acid and silver nitrate
Mixed solution in carry out Argent grain deposition 10s, reaction temperature be 8 DEG C, then by deposit complete polysilicon silicon chip be placed in hydrogen fluorine
The mixed solution of acid and hydrogen peroxide carries out chemical attack 500s, and reaction temperature is 60 DEG C, obtains nano black silicon sample；
60s is embathed Step 3: then black silicon sample is placed in the mixed liquor of ammoniacal liquor, hydrogen peroxide and monoethanolamine, reaction temperature
Spend for 8 DEG C；The mixed liquor that washed black silicon is placed in into hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride again embathes black silicon again
600s, reaction temperature is 80 DEG C；The last mixed liquor in ammoniacal liquor and hydrogen peroxide cleans black silicon face, and reaction temperature is 8 DEG C, reaction
Time is 30s；
Step 4: being cleaned in HF solution, then using pure water cleaning, finally dried using drier.It is black after reconstruct
Silicon face SEM image is as shown in Figure 1.
Hydrofluoric acid and HNO in the step one3Mixed solution in, the volume fraction of hydrofluoric acid is 12%, HNO3Volume
Fraction 60%, pure water volume fraction 28%, reaction temperature is 7 DEG C, and the reaction time is 2min.
In the step 2, percent concentration proportioning is in the mixed solution of hydrofluoric acid and silver nitrate, pure water 92%, hydrogen fluorine
Acid 3% and silver nitrate 5%；Percent concentration proportioning is in the mixed liquor of hydrofluoric acid and hydrogen peroxide, pure water 85%, hydrogen peroxide 5%
With hydrofluoric acid 10%.
In the step 3, the mixed liquor containing hydrogen peroxide and monoethanolamine, its percent concentration proportioning is pure water 68%, second
Hydramine 2%, ammoniacal liquor 10% and hydrogen peroxide 20%；Hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percentage are dense
Degree proportioning is pure water 73%, hydrogen peroxide 7%, hydrofluoric acid 3%, metaphosphoric acid 2% and ammonium fluoride 15%；Hydrogen peroxide and ammoniacal liquor mixing
Liquid, its percent concentration proportioning is pure water 70%, hydrogen peroxide 20% and ammoniacal liquor 10%.
HF volume fraction is 4% in the step 4, and the volume fraction of pure water is 96%, and scavenging period scope is 50s,
Pure water scavenging period scope is 90s.
Embodiment 2
A kind of manufacture method of polycrystalline surface inverted pyramid structure texture, comprises the following steps：
Step 1: from p-type polysilicon material, specification is 156cm*156cm, thickness is 200um, and polysilicon silicon chip is put
In hydrofluoric acid and HNO3Mixed solution in corrode, carry out surface mechanical damage layer removal；
Step 2: carry out black silicon making with metal ion auxiliary etch method method, by polysilicon silicon chip be placed in hydrofluoric acid and
Argent grain deposition 50s is carried out in the mixed solution of silver nitrate, reaction temperature is 20 DEG C, then the silicon chip for depositing completion is placed in into hydrogen fluorine
The mixed solution of acid and hydrogen peroxide carries out chemical attack 300s, and reaction temperature is 40 DEG C, obtains nano black silicon sample；
300s is embathed Step 3: then black silicon sample is placed in the mixed liquor of ammoniacal liquor, hydrogen peroxide and monoethanolamine, reaction temperature
Spend for 20 DEG C；The mixed liquor that washed black silicon is placed in into hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride again embathes black silicon again
300s, reaction temperature is 50 DEG C；The last mixed liquor in ammoniacal liquor and hydrogen peroxide cleans black silicon face, and reaction temperature is 20 DEG C, instead
It is 100s between seasonable；
Step 4: being cleaned in HF solution, then using pure water cleaning, finally dried using drier.
Hydrofluoric acid and HNO in the step one3Mixed solution in, the volume fraction of hydrofluoric acid is 13%, HNO3 body
Fraction 60%, pure water volume fraction 28%, reaction temperature is 8 DEG C, and the reaction time is 1.5min.
In the step 2, percent concentration proportioning is in the mixed solution of hydrofluoric acid and silver nitrate, pure water 96.9%, hydrogen
Fluoric acid 0.1% and silver nitrate 3%；Percent concentration proportioning is in the mixed liquor of hydrofluoric acid and hydrogen peroxide, pure water 90%, hydrogen peroxide
3% and hydrofluoric acid 7%.
In the step 3, the mixed liquor containing hydrogen peroxide and monoethanolamine, its percent concentration proportioning is pure water 75%, second
Hydramine 1%, ammoniacal liquor 7% and hydrogen peroxide 17%；Hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percent concentration
Match as pure water 80%, hydrogen peroxide 5%, hydrofluoric acid 1%, metaphosphoric acid 1% and ammonium fluoride 13%；Hydrogen peroxide and ammonia water mixture,
Its percent concentration proportioning is pure water 80%, hydrogen peroxide 15% and ammoniacal liquor 5%.
In the step 4, HF volume fraction is 1%, and the volume fraction of pure water is 99%, and scavenging period scope is
70s, pure water scavenging period scope is 70s
Embodiment 3
A kind of manufacture method of polycrystalline surface inverted pyramid structure texture, comprises the following steps：
Step 1: from p-type polysilicon material, specification is 156cm*156cm, thickness is 200um, and polysilicon silicon chip is put
In hydrofluoric acid and HNO3Mixed solution in corrode, carry out surface mechanical damage layer removal；
Step 2: carry out black silicon making with metal ion auxiliary etch method method, by polysilicon silicon chip be placed in hydrofluoric acid and
Argent grain deposition 50s is carried out in the mixed solution of silver nitrate, reaction temperature is 20 DEG C, then the silicon chip for depositing completion is placed in into hydrogen fluorine
The mixed solution of acid and hydrogen peroxide carries out chemical attack 300s, and reaction temperature is 40 DEG C, obtains nano black silicon sample；
300s is embathed Step 3: then black silicon sample is placed in the mixed liquor of ammoniacal liquor, hydrogen peroxide and monoethanolamine, reaction temperature
Spend for 20 DEG C；The mixed liquor that washed black silicon is placed in into hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride again embathes black silicon again
300s, reaction temperature is 50 DEG C；The last mixed liquor in ammoniacal liquor and hydrogen peroxide cleans black silicon face, and reaction temperature is 20 DEG C, instead
It is 100s between seasonable；
Step 4: being cleaned in HF solution, pure water cleaning is dried using drier.
Hydrofluoric acid and HNO in the step one3Mixed solution in, the volume fraction of hydrofluoric acid is 14%, HNO3Volume
Fraction 64%, pure water volume fraction 22%, reaction temperature is 9 DEG C, and the reaction time is 1min.
In the step 2, percent concentration proportioning is in the mixed solution of hydrofluoric acid and silver nitrate, pure water 97.9%, hydrogen
Fluoric acid 2% and silver nitrate 0.1%；Percent concentration proportioning is in the mixed liquor of hydrofluoric acid and hydrogen peroxide, pure water 95%, hydrogen peroxide
2% and hydrofluoric acid 3%.
In the step 3, the mixed liquor containing hydrogen peroxide and monoethanolamine, its percent concentration proportioning is pure water 80%, second
Hydramine 1%, ammoniacal liquor 5% and hydrogen peroxide 14%；Hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percent concentration
Match as pure water 85%, hydrogen peroxide 4%, hydrofluoric acid 0.5%, metaphosphoric acid 0.5% and ammonium fluoride 10%；Hydrogen peroxide and ammoniacal liquor mixing
Liquid, its percent concentration proportioning is pure water 90%, hydrogen peroxide 8% and ammoniacal liquor 2%.
In the step 4, HF volume fraction is 2%, and the volume fraction of pure water is 98%, and scavenging period scope is
90s, pure water scavenging period scope is 50s.
Embodiment 4
A kind of manufacture method of polycrystalline surface inverted pyramid structure texture, comprises the following steps：
Step 1: from p-type polysilicon material, specification is 156cm*156cm, thickness is 200um, and polysilicon silicon chip is put
In hydrofluoric acid and HNO3Mixed solution in corrode 3min, carry out surface mechanical damage layer removal；
Step 2: carry out black silicon making with metal ion auxiliary etch method method, by polysilicon silicon chip be placed in hydrofluoric acid and
Argent grain deposition 100s is carried out in the mixed solution of silver nitrate, reaction temperature is 30 DEG C, then the silicon chip for depositing completion is placed in into hydrogen
The mixed solution of fluoric acid and hydrogen peroxide carries out chemical attack 120s, and reaction temperature is 8 DEG C, obtains nano black silicon sample；
500s is embathed Step 3: then black silicon sample is placed in the mixed liquor of ammoniacal liquor, hydrogen peroxide and monoethanolamine, reaction temperature
Spend for 30 DEG C；The mixed liquor that washed black silicon is placed in into hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride again embathes black silicon again
50s, reaction temperature is 50 DEG C；The last mixed liquor in ammoniacal liquor and hydrogen peroxide cleans black silicon face, and reaction temperature is 30 DEG C, reaction
Time is 180s；
Step 4: being cleaned in HF solution, pure water cleaning is dried using drier.
Hydrofluoric acid and HNO in the step one3Mixed solution in, the volume fraction of hydrofluoric acid is 15%, HNO3Volume
Fraction 65%, pure water volume fraction 20%, reaction temperature is 7 DEG C, and the reaction time is 1min.
In the step 2, percent concentration proportioning is in the mixed solution of hydrofluoric acid and silver nitrate, pure water 99%, hydrogen fluorine
Acid 0.5% and silver nitrate 0.5%；Percent concentration proportioning is in the mixed liquor of hydrofluoric acid and hydrogen peroxide, pure water 98%, hydrogen peroxide
1% and hydrofluoric acid 1%.
In the step 3, the mixed liquor containing hydrogen peroxide and monoethanolamine, its percent concentration proportioning is pure water 97%, second
Hydramine 0%, ammoniacal liquor 3% and hydrogen peroxide 7%；Hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percent concentration
Match as pure water 90%, hydrogen peroxide 4%, hydrofluoric acid 0.1%, metaphosphoric acid 0.5% and ammonium fluoride 5.4%；Hydrogen peroxide and ammoniacal liquor are mixed
Liquid is closed, its percent concentration proportioning is pure water 97%, hydrogen peroxide 2% and ammoniacal liquor 1%.
In the step 4, HF volume fraction is 4%, and the volume fraction of pure water is 96%, and scavenging period scope is
60s, pure water scavenging period scope is 110s.
Embodiment 5
A kind of manufacture method of polycrystalline surface inverted pyramid structure texture, comprises the following steps：
Step 1: from p-type polysilicon material, specification is 156cm*156cm, thickness is 200um, and polysilicon silicon chip is put
In hydrofluoric acid and HNO3Mixed solution in corrode 3min, carry out surface mechanical damage layer removal；
Step 2: carry out black silicon making with metal ion auxiliary etch method method, by polysilicon silicon chip be placed in hydrofluoric acid and
Argent grain deposition 100s is carried out in the mixed solution of silver nitrate, reaction temperature is 30 DEG C, then the silicon chip for depositing completion is placed in into hydrogen
The mixed solution of fluoric acid and hydrogen peroxide carries out chemical attack 120s, and reaction temperature is 8 DEG C, obtains nano black silicon sample；
500s is embathed Step 3: then black silicon sample is placed in the mixed liquor of ammoniacal liquor, hydrogen peroxide and monoethanolamine, reaction temperature
Spend for 30 DEG C；The mixed liquor that washed black silicon is placed in into hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride again embathes black silicon again
50s, reaction temperature is 50 DEG C；The last mixed liquor in ammoniacal liquor and hydrogen peroxide cleans black silicon face, and reaction temperature is 30 DEG C, reaction
Time is 180s；
Step 4: being cleaned in HF solution, then using pure water cleaning, dried using drier.
Hydrofluoric acid and HNO in the step one3Mixed solution in, the volume fraction of hydrofluoric acid is 15%, HNO3Volume
Fraction 65%, pure water volume fraction 20%, reaction temperature is 7 DEG C, and the reaction time is 1min.
In the step 2, percent concentration proportioning is in the mixed solution of hydrofluoric acid and silver nitrate, pure water 99%, hydrogen fluorine
Acid 0.5% and silver nitrate 0.5%；Percent concentration proportioning is in the mixed liquor of hydrofluoric acid and hydrogen peroxide, pure water 98%, hydrogen peroxide
1% and hydrofluoric acid 1%.
In the step 3, the mixed liquor containing hydrogen peroxide and monoethanolamine, its percent concentration proportioning is pure water 97%, second
Hydramine 0%, ammoniacal liquor 1% and hydrogen peroxide 2%；Hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percent concentration
Match as pure water 94.9%, hydrogen peroxide 4%, hydrofluoric acid 0.1%, metaphosphoric acid 0% and ammonium fluoride 1%；Hydrogen peroxide and ammoniacal liquor mixing
Liquid, its percent concentration proportioning is pure water 97%, hydrogen peroxide 2% and ammoniacal liquor 1%.
In the step 4, HF volume fraction is 2%, and the volume fraction of pure water is 98%, and scavenging period scope is
80s, pure water scavenging period scope is 100s.
Embodiment 6
A kind of manufacture method of polycrystalline surface inverted pyramid structure texture, comprises the following steps：
Step 1: from p-type polysilicon material, specification is 156cm*156cm, thickness is 200um, and polysilicon silicon chip is put
In hydrofluoric acid and HNO3Mixed solution in corrode, carry out surface mechanical damage layer removal；
Step 2: carrying out black silicon making with laser pulse method, polysilicon silicon chip formation mask layer is formed on mask layer
Predetermined pattern via-hole array, is performed etching to graphic mask silicon chip, and predetermined pattern groove array is formed on silicon chip, removes mask
Layer, polysilicon silicon chip is placed in hydrogen sulfide gas, using the laser of 400 wavelength, and its pulse is 2100 irradiation silicon chips, is obtained
Nano black silicon sample；
Step 3: the mixed liquor of black silicon sample hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride is then embathed into black silicon again
600s, reaction temperature is 80 DEG C；
Step 4: being cleaned in HF solution, then using pure water cleaning, dried using drier.Black silicon table after reconstruct
Face SEM image is as shown in Figure 1.
Hydrofluoric acid and HNO in the step one3Mixed solution in, the volume fraction of hydrofluoric acid is 12%, HNO3Volume
Fraction 60%, pure water volume fraction 28%, reaction temperature is 7 DEG C, and the reaction time is 2min.
In the step 3, hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percent concentration proportioning is
Pure water 73%, hydrogen peroxide 7%, hydrofluoric acid 3%, metaphosphoric acid 2% and ammonium fluoride 15%.
In the step 4, HF volume fraction is 3%, and the volume fraction of pure water is 97%, and scavenging period scope is
100s, pure water scavenging period scope is 80s.
Embodiment 7
A kind of manufacture method of polycrystalline surface inverted pyramid structure texture, comprises the following steps：
Step 1: from p-type polysilicon material, specification is 156cm*156cm, thickness is 200um, and polysilicon silicon chip is put
In hydrofluoric acid and HNO3Mixed solution in corrode 3min, carry out surface mechanical damage layer removal；
Step 2: carrying out black silicon making with laser pulse method, polysilicon silicon chip formation mask layer is formed on mask layer
Predetermined pattern via-hole array, is performed etching to graphic mask silicon chip, and predetermined pattern groove array is formed on silicon chip, removes mask
Layer, polysilicon silicon chip is placed in sulfur hexafluoride gas, using the laser of 1000 wavelength, and its pulse is 500 irradiation silicon chips, is obtained
To nano black silicon sample；
Step 3: the mixed liquor that black silicon sample then is placed in into hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride embathes again
Black silicon 50s, reaction temperature is 50 DEG C；
Step 4: cleaning 1min in HF solution, then 1min is cleaned using pure water, finally dried using drier.
Hydrofluoric acid and HNO in the step one3Mixed solution in, the volume fraction of hydrofluoric acid is 15%, HNO3Volume
Fraction 65%, pure water volume fraction 20%, reaction temperature is 7 DEG C, and the reaction time is 1min.
In the step 3, hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percent concentration proportioning is
Pure water 90%, hydrogen peroxide 4%, hydrofluoric acid 0.1%, metaphosphoric acid 0.5% and ammonium fluoride 5.4%.
In the step 4, HF volume fraction is 3%, and the volume fraction of pure water is 97%, and scavenging period scope is
100s, pure water scavenging period scope is 80s.
Embodiment 8
A kind of manufacture method of polycrystalline surface inverted pyramid structure texture, comprises the following steps：
Step 1: from p-type polysilicon material, specification is 156cm*156cm, thickness is 200um, and polysilicon silicon chip is put
In hydrofluoric acid and HNO3Mixed solution in corrode, carry out surface mechanical damage layer removal；
Step 2: carrying out black silicon making with laser pulse method, polysilicon silicon chip formation mask layer is formed on mask layer
Predetermined pattern via-hole array, is performed etching to graphic mask silicon chip, and predetermined pattern groove array is formed on silicon chip, removes mask
Layer, polysilicon silicon chip is placed in sulfur hexafluoride gas, using the laser of 800 wavelength, and its pulse is 1500 irradiation silicon chips, is obtained
To nano black silicon sample；
Step 3: the mixed liquor that black silicon sample then is placed in into hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride embathes again
Black silicon 300s, reaction temperature is 50 DEG C；
Step 4: being cleaned in HF solution, then using pure water cleaning, finally dried using drier.
Hydrofluoric acid and HNO in the step one3Mixed solution in, the volume fraction of hydrofluoric acid is 14%, HNO3Volume
Fraction 64%, pure water volume fraction 22%, reaction temperature is 9 DEG C, and the reaction time is 1min.
In the step 3, hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percent concentration proportioning is
Pure water 85%, hydrogen peroxide 4%, hydrofluoric acid 0.5%, metaphosphoric acid 0.5% and ammonium fluoride 10%.
In the step 4, HF volume fraction is 1%, and the volume fraction of pure water is 99%, and scavenging period scope is
120s, pure water scavenging period scope is 40s.
Embodiment 9
A kind of manufacture method of polycrystalline surface inverted pyramid structure texture, comprises the following steps：
Step 1: from p-type polysilicon material, specification is 156cm*156cm, thickness is 200um, and polysilicon silicon chip is put
In hydrofluoric acid and HNO3Mixed solution in corrode 3min, carry out surface mechanical damage layer removal；
Step 2: carrying out black silicon making with reactive ion etching method, polysilicon silicon chip is placed in vacuum chamber, with low energy from
Polysilicon silicon chip after irradiation, is then placed in reactive ion etching vacuum chamber by beamlet uniform irradiation polysilicon silicon chip, is made
Black silicon sample；
500s is embathed Step 3: then black silicon sample is placed in the mixed liquor of ammoniacal liquor, hydrogen peroxide and monoethanolamine, reaction temperature
Spend for 30 DEG C；The mixed liquor that washed black silicon is placed in into hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride again embathes black silicon again
50s, reaction temperature is 50 DEG C；
Step 4: being cleaned in HF solution, then using pure water cleaning, finally dried using drier.
Hydrofluoric acid and HNO in the step one3Mixed solution in, the volume fraction of hydrofluoric acid is 15%, HNO3Volume
Fraction 65%, pure water volume fraction 20%, reaction temperature is 7 DEG C, and the reaction time is 1min.
In the step 3, hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percent concentration proportioning is
Pure water 94.9%, hydrogen peroxide 4%, hydrofluoric acid 0.1%, metaphosphoric acid 0% and ammonium fluoride 1%.
In the step 4, HF volume fraction is 5%, and the volume fraction of pure water is 95%, and scavenging period scope is
40s, pure water scavenging period scope is 120s.
Making in step 2 of the present invention on black silicon, can also use other existing preparation methods.
A kind of polysilicon surface inverted pyramid structure, polysilicon silicon chip surface has several inverted pyramid structures, each falls
Pyramid structure is shown as square aperture on the surface of polysilicon silicon chip, along four sides of square aperture respectively into polysilicon chip
Portion tilts extension, and four tapered planars connect the taper to form inverted pyramid structure；The side of the square aperture of inverted pyramid structure
A length of 100-1000 nanometers, vertical depth is 50-800 nanometers, its inclined tapered planar normal and polysilicon silicon chip upper surface
Angle between normal is 20-65 degree；On polysilicon silicon chip surface, inverted pyramid structure is random distribution, and each other
There is superposition.
Comparative example 1
Comparative example 1 is the nano black silicon structure do not reprocessed, SEM image as shown in Fig. 2 directly being entered using the black silicon
Row battery makes, and its complex centre can be very more, seriously reduce battery efficiency.
Comparative example 2
Conventional polysilicon surface texture preparation method process is as follows：Using hydrofluoric acid, nitric acid and pure water mixed liquor to original
Silicon chip carries out suede structure making, then silicon chip surface is cleaned with certain density alkali, and hydrofluoric acid pickling is finally passed through again
After washing.
Conventional black silicon face reflectivity is 24% in test comparison example 2, and SEM image is as shown in Figure 3.
The above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of polysilicon surface inverted pyramid structure, it is characterised in that comprise the following steps：
Step 1: polysilicon damaged layer on surface of silicon slice is removed：Polysilicon silicon chip after over cleaning is placed in hydrofluoric acid and HNO3's
In mixed solution, surface mechanical damage layer removal is carried out；
Step 2: the black silicon structure of polysilicon silicon chip surface makes：Using metal ion auxiliary etch method or use femtosecond laser arteries and veins
Rush method or reactive ion etching method carries out black silicon making；
Step 3: the making of polysilicon silicon chip surface inverted pyramid texture：First the black silicon of the above method is placed in containing dioxygen
Embathed in the mixed liquor of water and monoethanolamine, washed black silicon is then placed in the mixed of hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride
Liquid is closed to embathe again；Or only black silicon is placed in hydrogen peroxide, hydrofluoric acid, metaphosphoric acid and ammonium fluoride mixed liquor embathe；Can be
Inverted pyramid structure is made in polysilicon silicon chip surface；
In the step 3, the mixed liquor containing hydrogen peroxide and monoethanolamine, its percent concentration proportioning for pure water 68%-97%,
Monoethanolamine 0%-2%, ammoniacal liquor 1%~10% and hydrogen peroxide 2%-20%, reaction temperature are 8 DEG C -30 DEG C, and the reaction time is 60s-
500s；Hydrogen peroxide, hydrofluoric acid, the mixed liquor of metaphosphoric acid and ammonium fluoride, its percent concentration proportioning is pure water 73%-94.9%,
Hydrogen peroxide 4%-7%, hydrofluoric acid 0.1%-3%, metaphosphoric acid 0%-2% and ammonium fluoride 1%-15%, reaction temperature are 50 DEG C -80
DEG C, the reaction time is 50s-600s；
Step 4: the cleaning of polysilicon silicon chip：The polysilicon silicon chip that surface has inverted pyramid structure is cleaned in HF solution,
Pure water cleaning is placed into, is finally dried.
2. the preparation method of polysilicon surface inverted pyramid structure according to claim 1, it is characterised in that：The step
Hydrofluoric acid and HNO in one3Mixed solution in, the volume fraction of hydrofluoric acid is 12%~15%, HNO3Volume fraction 60%~
65%, pure water volume fraction 20%~28%, reaction temperature is 7~9 DEG C, and the reaction time is 1-2min.
3. the preparation method of polysilicon surface inverted pyramid structure according to claim 1, it is characterised in that：The step
Metal ion auxiliary etch method in two：The polysilicon silicon chip removed after damage layer is placed in the mixed solution of hydrofluoric acid and silver nitrate
Middle progress Argent grain deposition, then the polysilicon silicon chip that deposition is completed are placed in the mixed solution of hydrofluoric acid and hydrogen peroxide and changed
Corrosion is learned, nano black silicon is obtained.
4. the preparation method of polysilicon surface inverted pyramid structure according to claim 3, it is characterised in that：The step
In two metal ion auxiliary etch methods, percent concentration proportioning is in the mixed solution of hydrofluoric acid and silver nitrate, pure water 92%-
99%th, hydrofluoric acid 0.1%~3% and silver nitrate 0.1%~5%, reaction temperature be 8 DEG C -30 DEG C, the reaction time be 10~
100s；Percent concentration proportioning is in the mixed liquor of hydrofluoric acid and hydrogen peroxide, pure water 85%-98%, hydrogen peroxide 1%-5% and hydrogen
Fluoric acid 1%-10%, reaction temperature is 8 DEG C -60 DEG C, and the reaction time is 120s-500s.
5. the preparation method of polysilicon surface inverted pyramid structure according to claim 1, it is characterised in that：The step
Femto-second laser pulse method in two：Black silicon making is carried out with laser pulse method, by polysilicon silicon chip formation mask layer, on mask layer
Predetermined pattern via-hole array is formed, graphic mask polysilicon silicon chip is performed etching, predetermined pattern is formed on polysilicon silicon chip
Groove array, removes mask layer, polysilicon silicon chip is placed in sulfur hexafluoride or hydrogen sulfide gas, 400-1000 wavelength is used
Laser, its pulse is 500-2100 irradiation silicon chip, obtains nano black silicon.
6. the preparation method of polysilicon surface inverted pyramid structure according to claim 1, it is characterised in that：The step
Reactive ion etching method in two：Polysilicon silicon chip is placed in vacuum chamber, with low energy ion beam uniform irradiation polysilicon silicon chip, so
The polysilicon silicon chip after irradiation is placed in reactive ion etching vacuum chamber afterwards, black silicon sample is made.
7. the preparation method of polysilicon surface inverted pyramid structure according to claim 1, it is characterised in that：By step 3
Obtained surface there is the polysilicon silicon chip of inverted pyramid structure to insert again in the mixed liquor of ammoniacal liquor and hydrogen peroxide clean, then carry out
Step 4, the mixed liquor of the ammoniacal liquor and hydrogen peroxide, its percent concentration proportioning for pure water 70%~97%, hydrogen peroxide 2%~
20% and ammoniacal liquor 1%~10%, reaction temperature is 8 DEG C -30 DEG C, and the reaction time is 30~180s.
8. the preparation method of polysilicon surface inverted pyramid structure according to claim 7, it is characterised in that：The step
HF volume fraction is 1%~5% in four, and the volume fraction of pure water is 95%~99%, and scavenging period scope is 40~120s,
Pure water scavenging period scope is 40~120s.
9. the polysilicon surface inverted pyramid structure prepared according to any described preparation methods of claim 1-8, it is special
Levy and be：Polysilicon silicon chip surface has several inverted pyramid structures, and each inverted pyramid structure is on the surface of polysilicon silicon chip
Square aperture is shown as, is extended respectively to polysilicon chip inner inclination along four sides of square aperture, four tapered planar connections
Form the taper of inverted pyramid structure；The length of side of the square aperture of inverted pyramid structure is 100-1000 nanometers, vertical depth is
50-800 nanometers, the angle between its inclined tapered planar normal and polysilicon silicon chip surface normal is 20-65 degree；In polycrystalline
On silicon silicon chip surface, inverted pyramid structure is random distribution, and has superposition each other.
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| CN105274626B (en) * | 2015-10-10 | 2017-12-01 | 浙江晶科能源有限公司 | A kind for the treatment of fluid and processing method for being used to optimize black silicon face structure |
| CN105702803A (en) * | 2015-12-21 | 2016-06-22 | 合肥晶澳太阳能科技有限公司 | Process for manufacturing efficient polycrystalline cell |
| CN105449045B (en) * | 2015-12-29 | 2017-03-22 | 江西比太科技有限公司 | Surface micro corrosion cleaning method applicable for crystal silicon wafer after RIE (Reactive Ion Etching) texturing |
| CN106505113B (en) * | 2016-11-11 | 2018-08-24 | 苏州晶牧光材料科技有限公司 | The matte preparation method of crystal-silicon solar cell |
| CN108511539B (en) * | 2017-02-28 | 2020-02-04 | 比亚迪股份有限公司 | Preparation method of solar cell |
| CN106997915A (en) * | 2017-04-01 | 2017-08-01 | 江苏辉伦太阳能科技有限公司 | A kind of monocrystalline silicon surface honey comb structure and preparation method thereof |
| CN107068805A (en) * | 2017-04-01 | 2017-08-18 | 江苏辉伦太阳能科技有限公司 | A kind of polysilicon surface honey comb structure and preparation method thereof |
| CN107895744A (en) * | 2017-11-10 | 2018-04-10 | 中国科学院物理研究所 | A kind of polysilicon chip for solar cell and preparation method thereof |
| CN110265499A (en) * | 2019-05-28 | 2019-09-20 | 中国科学院物理研究所 | Silicon wafer and its preparation method and application with suede structure |
| CN110993743A (en) * | 2019-12-25 | 2020-04-10 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of heterojunction photovoltaic device |
| CN111323957A (en) * | 2020-01-15 | 2020-06-23 | 武汉大学 | Color flexible display module and preparation method thereof |
| CN113707740A (en) * | 2020-05-06 | 2021-11-26 | 南京理工大学 | Preparation method of black silicon material |
| CN113512229B (en) * | 2021-07-02 | 2022-10-14 | 中国科学院重庆绿色智能技术研究院 | Micro-nano porous light trapping structure and preparation method thereof |
| CN113707764A (en) * | 2021-08-27 | 2021-11-26 | 福建金石能源有限公司 | Manufacturing method of solar cell adopting inverted pyramid suede |
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