CN107419336A - A kind of Cu bases nano black silicon flocking additive preparation method - Google Patents
A kind of Cu bases nano black silicon flocking additive preparation method Download PDFInfo
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- CN107419336A CN107419336A CN201710597588.7A CN201710597588A CN107419336A CN 107419336 A CN107419336 A CN 107419336A CN 201710597588 A CN201710597588 A CN 201710597588A CN 107419336 A CN107419336 A CN 107419336A
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- Prior art keywords
- black silicon
- preparation
- flocking additive
- nano
- copper
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- 239000000654 additive Substances 0.000 title claims abstract description 51
- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 46
- 230000000996 additive effect Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000010949 copper Substances 0.000 claims abstract description 76
- 239000002245 particle Substances 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 claims abstract description 44
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 claims abstract description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000005749 Copper compound Substances 0.000 claims abstract description 12
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 4
- 229930003268 Vitamin C Natural products 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019154 vitamin C Nutrition 0.000 claims description 4
- 239000011718 vitamin C Substances 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- -1 alcohol ester Chemical class 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 235000008216 herbs Nutrition 0.000 abstract description 21
- 210000002268 wool Anatomy 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 235000019441 ethanol Nutrition 0.000 description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 23
- 229910052710 silicon Inorganic materials 0.000 description 23
- 239000010703 silicon Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 7
- 238000002310 reflectometry Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 229910020479 SiO2+6HF Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- 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
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a kind of Cu bases nano black silicon flocking additive preparation method.The preparation method is as follows：1) copper compound is dissolved in ethanol solution, after adding reducing agent, dispersant, stirring, disperseed；2) reacted after adding silane coupler；3) filter, wash, dry, pulverize, grind, sieve, selection obtains nano copper particle；4) obtained nano copper particle is mixed with ethanol, reducing agent, ammoniacal liquor, adds deionized water to supply, obtain a nanometer flocking additive.The present invention for that can substantially reduce Material Cost in black silicon making herbs into wool, while has good making herbs into wool effect, formation matte yardstick is small, the good no color differnece of uniformity again by the use of nanometer Cu particles as the black silicon flocking additive main raw material(s) of metal auxiliary catalysis.
Description
Technical field
The present invention relates to solar cell manufacturing field, and in particular to a kind of Cu bases nano black silicon flocking additive preparation side
Method.
Background technology
Black silicon (blacksilicon) refers to almost absorb the extremely low silicon face of all visible rays, reflectivity or silicon substrate
Film, it is a kind of novel semiconductor material that can greatly improve photoelectric transformation efficiency that current research is found.With in general silicon material
Material is compared, and black silicon material can almost stick all visible rays, therefore outward appearance appears to be black；And its surface texture is to have
The taper microstructure of sequence, photon will not be directly reflected after entering the structure, but silicon is entered after multiple reflections
Inside body, reduce the reflection of light, improve the utilization rate of light.Because black silicon material has excellent antireflective properties, therefore
There is important application prospect in photovoltaic art.
In photovoltaic module cost, silicon chip cost accounts for more than 50%, and silicon chip cost reduces to photovoltaic module holistic cost, from
And the paces for accelerating par online are significant.Silicon chip cost more than 20% can effectively be reduced using Buddha's warrior attendant wire cutting polycrystalline,
Being advantageous to photovoltaic products reduces cost, realizes that photovoltaic par is surfed the Net early.But diamond wire sliced crystal silicon chip, mechanical damage is small,
Effective matte nuclearing centre can not be formed, poor with effect after classical acid making herbs into wool method, silicon chip reflectivity is high, irregular colour is even, from
And influence component generated energy.So needing to use nanometer flocking additive, applied to crystal silicon chip process for etching, nano black is formed
Silicon matte, matte is uniform, and technique is controllable, and reflectivity is low.Meanwhile by being adjusted to battery process whole matching, solve diffusion, plating
The problems such as film, silk-screen printing etc., realize that battery efficiency improves.
Flocking additive refers to during the process for etching of monocrystaline silicon solar cell, added with beneficial to reaction result and
The chemical assistant of properties of product.Black silicon making herbs into wool nanometer additive is mainly acted on using metal catalytic, far low in Ag/Si system capacities
In the valence band edge of silicon, Ag obtains electronics from the valence band of silicon, so as to be reduced.
Ag++e- VB→Ago(S)
Si+2H2O→SiO2+4H++4e-
H2O2Continue to aoxidize the silicon below Ag particles, accelerate the progress of above-mentioned reaction, while silica is corroded by hydrofluoric acid
Dissolve.
2H2O2+Si→SiO2+2H2O
SiO2+6HF→H2SiF6+2H2O
But existing black silicon making herbs into wool nanometer additive is more using Ag as metal auxiliary catalysis flocking additive main raw material(s), makes
The flocking additive cost obtained now remains high.
The content of the invention
To solve the above problems, the invention provides a kind of preparation method of Cu (copper) base nano black silicon flocking additive,
By the use of nanometer Cu particles as the black silicon flocking additive main raw material(s) of metal auxiliary catalysis, Material Cost is reduced, while have again very
Good making herbs into wool effect, formation matte yardstick is small, the good no color differnece of uniformity.
To realize the technical purpose, the technical scheme is that：A kind of system of Cu bases nano black silicon flocking additive
Preparation Method, the preparation method are as follows：
1) copper compound is dissolved in ethanol solution, after adding reducing agent, dispersant, stirring, disperseed；
2) silane coupler reaction is added；
According to percentage by weight, the copper compound, reducing agent, dispersant, the accounting of silane coupler for 10~20%,
0.5~10%, 10~50%, 0.1~1%, remaining is ethanol；
3) filter, wash, dry, pulverize, grind, sieve, selection obtains nano copper particle；
4) obtained nano copper particle is mixed with ethanol, reducing agent, ammoniacal liquor, obtains a nanometer flocking additive；
By weight percentage, the nano copper particle, ethanol, reducing agent, the accounting of ammoniacal liquor are respectively 5~20%, 5-
20%th, 1-3%, 10-20%, remaining is deionized water.
Preferably, the copper compound includes the one or more in copper chloride, copper sulphate, copper nitrate.But the copper
Conjunction is not limited to above-mentioned several.
Preferably, the reducing agent includes vitamin C, citric acid, glucose.
Preferably, the dispersant includes PVP, polyalcohol, oleic acid, fragrant alcohol ester.Dispersant also has protectant simultaneously
Effect, protective agent (dispersant) are adsorbed onto nano copper particle surface, prevent oxidation chemistry reaction from occurring, while prevent nano particle
Reunite.
Preferably, the silane coupler includes γ-r-chloropropyl trimethoxyl silane, VTES, three
Methoxy silane.
Preferably, the silane coupler is dissolved in ethanol solution.
Preferably, the stirring of the step 1) and it is scattered be normal temperature magnetic bar high-speed stirred 20-40 minutes, ultrasonic wave added point
Dissipate 5-20 minutes.
Preferably, the reaction condition of the step 2) is 60-100 DEG C of constant temperature high-speed stirred 3-5 hour.
Preferably, the drying of the step 3) is 80-120 DEG C of dry 6-10 hour.
Preferably, the nano copper particle of choosing is the nano copper particle for choosing diameter 20-100nm.
Preparation method of the present invention is specially：
1) percentage by weight 10-20% copper compound is added in ethanol solution, adds percentage by weight 0.5-10%
Reducing agent, add 10-50% dispersant, normal temperature magnetic bar high-speed stirred 20-40 minutes, ultrasonic wave added disperses 5-20 points
Clock；
2) ethanol solution of 0.1-1% silane couplers, 60-100 DEG C of constant temperature high-speed stirred 3-5 hour is added dropwise；
3) filter, absolute ethyl alcohol washing, centrifugal treating, 80-120 DEG C of dry 6-10 hour, crush, grind, sieving, choosing
20-100nm diameter nano copper particles；
4) the above-mentioned nano copper particles of 5-20% by weight percentage, 5-20% ethanol, 1-3% reducing agents, 10-20% ammoniacal liquor
Mixing is made into mixed solution, is supplemented to 100% with deionized water, is uniformly mixed, you can a nanometer flocking additive is made.
Need to consider that particle size is small in nano copper particle preparation process, uniform, good water solubility, good dispersion, be not easy oxygen
The factors such as change, so the present invention adds surface modifying material in nano copper particle preparation process, prevent nano particle macroface
Separation, and the microcosmic aggregation of nano particle is prevented, while increase the water-soluble and dispersed of nano particle.
The modified Nano copper particle of preparation is added in the chemical solution being necessarily formulated, forms black silicon flocking additive, energy
Ensure that nano copper particle is uniformly dispersed, dissolubility is good, and prevents nano copper particle from aoxidizing.
In the black silicon flocking additive of the present invention, ethanol and reducing agent (vitamin C, citric acid, glucose) prevent from receiving
The effect of rice copper oxidation, while reducing agent can also decompose bulky grain Nanometer Copper, improve the nano copper particle uniformity.Ammoniacal liquor can
Increase the dissolubility of nano copper particle, improve additive adhesion effect, advantageously form the suede structure of even porous.
Flocking additive of the present invention is directed to black silicon etching method, using Cu as metallic catalyst, itself is not involved in reacting,
The place reaction for having nano copper particle is accelerated, and so as to form pore space structure, reduces reflectivity.
The beneficial effects of the present invention are：
1st, by the use of nanometer Cu particles as the black silicon flocking additive main raw material(s) of metal auxiliary catalysis, substantially reduce material into
This, so as to reduce making herbs into wool cost, is advantageous to the development of photovoltaic industry.
2nd, silicon chip surface making herbs into wool is carried out using this flocking additive, formation matte yardstick is small, the good no color differnece of uniformity.
The present invention is directed to black silicon etching method, using Cu as metallic catalyst, for silicon wafer cut by diamond wire, is there is nanometer
The place reaction of copper particle is accelerated, and so as to form pore space structure, reduces reflectivity, formation matte yardstick is small, and uniformity is good colourless
Difference.Due to replacing silver to substantially reduce Material Cost, favorably as metal auxiliary catalysis flocking additive main raw material(s) using copper
In the development of photovoltaic industry.
Brief description of the drawings
Fig. 1 is the microscopic appearance figure of the application making herbs into wool of embodiment 1.
Fig. 2 is that the SEM of the application making herbs into wool of embodiment 1 schemes.
Fig. 3 is that the SEM of the application making herbs into wool of embodiment 2 schemes.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below.Obviously, described implementation
Example only part of the embodiment of the present invention, rather than whole embodiments.It is common based on the embodiment in the present invention, this area
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
The present invention provides a kind of Cu bases nano black silicon flocking additive preparation method, and the preparation method is as follows：1) by copper
Compound is dissolved in ethanol solution, after adding reducing agent, dispersant, stirring, is disperseed；
2) silane coupler reaction is added；
According to percentage by weight, the copper compound, reducing agent, dispersant, the accounting of silane coupler for 10~20%,
0.5~10%, 10~50%, 0.1~1%, remaining is ethanol；
It is furthermore preferred that according to percentage by weight, the copper compound, reducing agent, dispersant, the accounting of silane coupler are
15%th, 5%, 20%, 0.5%, remaining is ethanol；
3) filter, wash, dry, pulverize, grind, sieve, selection obtains nano copper particle；
4) obtained nano copper particle is mixed with ethanol, reducing agent, ammoniacal liquor, obtains a nanometer flocking additive；
By weight percentage, the nano copper particle, ethanol, reducing agent, the accounting of ammoniacal liquor are respectively 5~20%, 5-
20%th, 1-3%, 10-20%, remaining is deionized water；
It is furthermore preferred that by weight percentage, the nano copper particle, ethanol, reducing agent, the accounting of ammoniacal liquor are respectively
15%th, 20%, 1%, 20%, remaining is deionized water.
Preferably, the copper compound includes the one or more in copper chloride, copper sulphate, copper nitrate.But the copper
Conjunction is not limited to above-mentioned several.
Preferably, the reducing agent includes vitamin C, citric acid, glucose.
Preferably, the dispersant includes PVP, polyalcohol, oleic acid, fragrant alcohol ester.
Preferably, the silane coupler includes γ-r-chloropropyl trimethoxyl silane, VTES, three
Methoxy silane.
Preferably, the silane coupler is dissolved in ethanol solution.
Preferably, the stirring of the step 1) and it is scattered be normal temperature magnetic bar high-speed stirred 20-40 minutes, ultrasonic wave added point
Dissipate 5-20 minutes.
Preferably, the reaction condition of the step 2) is 60-100 DEG C of constant temperature high-speed stirred 3-5 hour.
Preferably, the drying of the step 3) is 80-120 DEG C of dry 6-10 hour.
Preferably, the nano copper particle of choosing is the nano copper particle for choosing diameter 20-100nm.
Specifically, the step of preparation method of the present invention, is：
1) percentage by weight 10-20% copper compound is added in ethanol solution, adds percentage by weight 0.5-10%
Reducing agent, add 10-50% dispersant, normal temperature magnetic bar high-speed stirred 20-40 minutes, ultrasonic wave added disperses 5-20 points
Clock；
2) ethanol solution of 0.1-1% silane couplers, 60-100 DEG C of constant temperature high-speed stirred 3-5 hour is added dropwise；
3) filter, absolute ethyl alcohol washing, centrifugal treating, 80-120 DEG C of dry 6-10 hour, crush, grind, sieving, choosing
20-100nm diameter nano copper particles；
4) the above-mentioned nano copper particles of 5-20% by weight percentage, 5-20% ethanol, 1-3% reducing agents, 10-20% ammoniacal liquor
Mixing is made into mixed solution, is supplemented to 100% with deionized water, is uniformly mixed, you can a nanometer flocking additive is made.
Embodiment 1
1. by the CuCl of percentage by weight 15%2It is dissolved in ethanol in proper amount, adds the citric acid of percentage by weight 5%,
Add 20%PVP (polyvinylpyrrolidone)；Normal temperature magnetic bar high-speed stirred 30 minutes, ultrasonic wave added are scattered 15 minutes；
2. 0.5% silane coupler being dissolved in ethanol is added dropwise, it is small to 100%, 80 DEG C of constant temperature high-speed stirred 4 to supply ethanol
When；
3. above-mentioned reaction system is filtered, absolute ethyl alcohol washing, centrifugal treating, 100 DEG C of drying 6 hours, crush, grind,
Sieving, choose 20-100nm diameter nano copper particles；
4. by weight percentage, 15% above-mentioned nanometer of Cu particle, 20% ethanol, 1% citric acid, 20% ammoniacal liquor are made into mixed
Solution is closed, 100% is complemented to deionized water, is uniformly mixed, you can Cu bases nano black silicon making herbs into wool addition of the present invention is made
Agent.
The above-mentioned Cu base nano black silicon flocking additives being prepared are used for making herbs into wool, main making herbs into wool process includes diamond wire
It is molten to cut silicon chip acetone, ethanol, ultra-pure water ultrasonic cleaning (degreasing and metal ion) → deionized water cleaning → 25%NaOH
85 DEG C of liquid cleaning 5min (removal surface damage layer) → deionized water cleaning → flocking additive of the present invention, HF (49%), go from
1: 20-50: 100 ratios are made into the aqueous solution to sub- water by volume, 6-20 DEG C, 1-10min (black silicon making herbs into wool) → 5-40%HNO3
(69%)+10-50%HF (49%) aqueous solution, 6-30 DEG C, 30-300s (reaming) → deionized water cleaning → HCl solution (removes gold
Belong to ion) → 5% dilute NaOH cleanings → deionized water cleaning.
This nanometer of flocking additive is applied to the preparation of black silicon cell, obtains the black silicon making herbs into wool table of reflectivity 15%
Face, as shown in Figure 1 and Figure 2, matte yardstick are small, and uniformity is good, no color differnece.
Embodiment 2
1. by the CuSO of percentage by weight 10%4Add in ethanol solution, add the citric acid of percentage by weight 0.5%,
Add 40%PVP；Normal temperature magnetic bar high-speed stirred 30 minutes, ultrasonic wave added are scattered 15 minutes；
2. being added dropwise 1.0% is dissolved in the silane coupler of ethanol, then complements to 100% with ethanol, 60 DEG C of constant temperature high-speed stirreds 4
Hour；
3. filtering, absolute ethyl alcohol washing, centrifugal treating, 80 DEG C of drying 6 hours, crush, grinding, sieving, selection 30-70nm
The nano copper particle of diameter.
Match somebody with somebody 4. by weight percentage, 13% above-mentioned nanometer of Cu particle, 15% ethanol, 2% citric acid, 10% ammoniacal liquor are mixed
Into mixed solution, 100% is complemented to deionized water, is uniformly mixed, you can a nanometer flocking additive is made.
The above-mentioned Cu base nano black silicon flocking additives being prepared are used for making herbs into wool, main making herbs into wool process includes diamond wire
Cut silicon chip acetone, ethanol, ultra-pure water and be cleaned by ultrasonic (degreasing and metal ion) → deionized water cleaning → 5%HNO3
(69%) 8 DEG C of cleaning 30s of+25%HF (49%) aqueous solution (removing surface damage layer, form etch pit) → deionized water cleaning
1: 20-50: 100 ratios are made into the aqueous solution by volume for → flocking additive of the present invention, HF (49%), deionized water, 6-20 DEG C,
1-10min (black silicon making herbs into wool) → 5-40%HNO3 (69%)+10-50%HF (49%) aqueous solution, 6-30 DEG C, 30-300s (expands
Hole) the dilute NaOH cleanings of → deionized water cleaning → HCl solution (removing metal ion) → 5% → deionized water cleaning.
This nanometer of flocking additive is applied to the preparation of black silicon cell, obtains the black silicon making herbs into wool table of reflectivity 15%
Face, as shown in figure 3, going to damage while after forming etch pit using acid corrosion method used, by black silicon flocking additive in etch pit
Interior to form the sunken light small structures of many 30-50nm, matte yardstick is small, the good no color differnece of uniformity.
Embodiment 3
1. by the CuCl of percentage by weight 20%2Add in ethanol solution, add the glucose of percentage by weight 10%, then
46% ethylene glycol, normal temperature magnetic bar high-speed stirred 40 minutes are added, ultrasonic wave added disperses 20 minutes；
2. being added dropwise 1% is dissolved in the silane coupler of ethanol, then complements to 100% with ethanol, 100 DEG C of constant temperature high-speed stirreds 3
Hour；
3. filtering, absolute ethyl alcohol washing, centrifugal treating, 120 DEG C of drying 6 hours, crush, grinding, sieving, selection 20-
60nm diameter nano copper particles；
Match somebody with somebody 4. by weight percentage, 5% above-mentioned nanometer of Cu particle, 15% ethanol, 3% citric acid, 20% ammoniacal liquor are mixed
Into mixed solution, 100% is complemented to deionized water, is uniformly mixed, you can Cu base nano black silicon flocking additives are made.
Embodiment 4
1. by the CuCl of percentage by weight 15%2Add in ethanol solution, add the citric acid of percentage by weight 7%, then
Add 40% propane diols；Normal temperature magnetic bar high-speed stirred 20 minutes, ultrasonic wave added are scattered 20 minutes；
2. the ethanol solution of 1% silane coupler is added dropwise, 100% is complemented to ethanol, 100 DEG C of constant temperature high-speed stirreds 5 are small
When；
3. filtering, absolute ethyl alcohol washing, centrifugal treating, 120 DEG C of drying 6 hours, crush, grinding, sieving, selection 20-
100nm diameter nano copper particles.
Match somebody with somebody 4. by weight percentage, 15% above-mentioned nanometer of Cu particle, 5% ethanol, 2% citric acid, 15% ammoniacal liquor are mixed
Into mixed solution, 100% is complemented to deionized water, is uniformly mixed, you can Cu base nano black silicon flocking additives are made.
Embodiment 5
1. by the CuCl of percentage by weight 15%2Add in ethanol solution, add the citric acid of percentage by weight 10%, then
Add 50% propane diols；Normal temperature magnetic bar high-speed stirred 20 minutes, ultrasonic wave added are scattered 20 minutes；
2. the ethanol solution of 1% silane coupler is added dropwise, 100% is complemented to ethanol, 100 DEG C of constant temperature high-speed stirreds 5 are small
When；
3. filtering, absolute ethyl alcohol washing, centrifugal treating, 120 DEG C of drying 6 hours, crush, grinding, sieving, selection 30-
80nm diameter nano copper particles.
Match somebody with somebody 4. by weight percentage, 10% above-mentioned nanometer of Cu particle, 20% ethanol, 1% citric acid, 10% ammoniacal liquor are mixed
Into mixed solution, 100% is complemented to deionized water, is uniformly mixed, you can Cu base nano black silicon flocking additives are made.
The silicon wafer cell piece prepared to embodiment 1~4 is tested, and parameters are as shown in table 1.
The performance parameter of silicon chip prepared by 1 each embodiment of table
From table 1, the silicon chip that is prepared using the present invention have excellent conversion efficiency (Eta), open-circuit voltage (Uoc),
Short circuit current (Isc), fill factor, curve factor (FF), there is the quality of the silicon chip prepared not less than Ag base nano black silicon flocking additive,
Ag base nano black silicon flocking additives can successfully be substituted.
The present invention substantially reduces thing by the use of nanometer Cu particles as the black silicon flocking additive main raw material(s) of metal auxiliary catalysis
Expect cost, while have good making herbs into wool effect again, formation matte yardstick is small, the good no color differnece of uniformity, and the silicon chip quality of preparation is good
It is good.
For the person of ordinary skill of the art, without departing from the concept of the premise of the invention, can also do
Go out several modifications and improvements, these belong to protection scope of the present invention.
Claims (9)
1. a kind of preparation method of Cu bases nano black silicon flocking additive, it is characterised in that the preparation method is as follows：
1) copper compound is dissolved in ethanol solution, after adding reducing agent, dispersant, stirring, disperseed；
2) silane coupler reaction is added；
According to percentage by weight, the copper compound, reducing agent, dispersant, the accounting of silane coupler are 10~20%, 0.5
~10%, 10~50%, 0.1~1%, remaining is ethanol；
3) filter, wash, dry, pulverize, grind, sieve, selection obtains nano copper particle；
4) obtained nano copper particle is mixed with ethanol, reducing agent, ammoniacal liquor, obtains a nanometer flocking additive；
By weight percentage, the nano copper particle, ethanol, reducing agent, the accounting of ammoniacal liquor are respectively 5~20%, 5-20%, 1-
3%th, 10-20%, remaining is deionized water.
2. the preparation method of Cu bases nano black silicon flocking additive as claimed in claim 1, it is characterised in that the copper chemical combination
Thing includes the one or more in copper chloride, copper sulphate, copper nitrate.
3. the preparation method of Cu bases nano black silicon flocking additive as claimed in claim 1, it is characterised in that the reducing agent
Including vitamin C, citric acid, glucose.
4. the preparation method of Cu bases nano black silicon flocking additive as claimed in claim 1, it is characterised in that the dispersant
Including PVP, polyalcohol, oleic acid, fragrant alcohol ester.
5. the preparation method of Cu bases nano black silicon flocking additive as claimed in claim 1, it is characterised in that the silane is even
Joining agent includes γ-r-chloropropyl trimethoxyl silane, VTES, trimethoxy silane.
6. the preparation method of Cu bases nano black silicon flocking additive as claimed in claim 1, it is characterised in that the step 1)
Stirring and it is scattered be normal temperature magnetic bar high-speed stirred 20-40 minutes, ultrasonic wave added disperses 5-20 minutes.
7. the preparation method of Cu bases nano black silicon flocking additive as claimed in claim 1, it is characterised in that the step 2)
Reaction condition be 60-100 DEG C of constant temperature high-speed stirred 3-5 hour.
8. the preparation method of Cu bases nano black silicon flocking additive as claimed in claim 1, it is characterised in that the step 3)
Drying be 80-120 DEG C of dry 6-10 hour.
9. the preparation method of Cu bases nano black silicon flocking additive as claimed in claim 1, it is characterised in that the selection is received
Rice copper particle is the nano copper particle for choosing diameter 20-100nm.
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| CN109680339A (en) * | 2019-02-15 | 2019-04-26 | 嘉兴尚能光伏材料科技有限公司 | Polysilicon chip acid texturing assistant agent and polysilicon chip acid etching method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009084091A (en) * | 2007-09-28 | 2009-04-23 | Sumco Corp | Etching liquid and method for manufacturing silicon wafer |
| CN104195645A (en) * | 2014-08-06 | 2014-12-10 | 中国科学院物理研究所 | Acidic texturing solution for etching solar cell silicon wafer, texturing method, solar cell silicon wafer and manufacturing method of solar cell silicon wafer |
| CN105810761A (en) * | 2016-04-29 | 2016-07-27 | 南京工业大学 | Texturing method of polycrystalline silicon wafer cut by diamond wire |
| CN106935669A (en) * | 2017-05-23 | 2017-07-07 | 江苏福吉食品有限公司 | A kind of etching method of the diamond wire section black silicon of polycrystalline |
-
2017
- 2017-07-20 CN CN201710597588.7A patent/CN107419336B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009084091A (en) * | 2007-09-28 | 2009-04-23 | Sumco Corp | Etching liquid and method for manufacturing silicon wafer |
| CN104195645A (en) * | 2014-08-06 | 2014-12-10 | 中国科学院物理研究所 | Acidic texturing solution for etching solar cell silicon wafer, texturing method, solar cell silicon wafer and manufacturing method of solar cell silicon wafer |
| CN105810761A (en) * | 2016-04-29 | 2016-07-27 | 南京工业大学 | Texturing method of polycrystalline silicon wafer cut by diamond wire |
| CN106935669A (en) * | 2017-05-23 | 2017-07-07 | 江苏福吉食品有限公司 | A kind of etching method of the diamond wire section black silicon of polycrystalline |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109680339A (en) * | 2019-02-15 | 2019-04-26 | 嘉兴尚能光伏材料科技有限公司 | Polysilicon chip acid texturing assistant agent and polysilicon chip acid etching method |
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