CN107419336B - Preparation method of Cu-based nano black silicon texturing additive - Google Patents
Preparation method of Cu-based nano black silicon texturing additive Download PDFInfo
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- 239000000654 additive Substances 0.000 title claims abstract description 47
- 230000000996 additive effect Effects 0.000 title claims abstract description 47
- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 134
- 239000010949 copper Substances 0.000 claims abstract description 68
- 239000002245 particle Substances 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005749 Copper compound Substances 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
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- 239000000243 solution Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
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- 239000000203 mixture Substances 0.000 claims description 10
- 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
- 230000001502 supplementing effect Effects 0.000 claims description 8
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- 239000008103 glucose Substances 0.000 claims description 5
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- 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
- 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
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-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
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- -1 aromatic alcohol ester Chemical class 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 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
- 238000009775 high-speed stirring Methods 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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
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- 230000000694 effects Effects 0.000 abstract description 6
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- 235000019441 ethanol Nutrition 0.000 description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 22
- 229910052710 silicon Inorganic materials 0.000 description 22
- 239000010703 silicon Substances 0.000 description 22
- 238000004140 cleaning Methods 0.000 description 15
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- 239000002105 nanoparticle Substances 0.000 description 9
- 238000002310 reflectometry Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 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
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
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- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 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
- 238000005520 cutting process Methods 0.000 description 2
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- 229910052682 stishovite Inorganic materials 0.000 description 2
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- 238000004506 ultrasonic cleaning Methods 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
- 230000000295 complement effect Effects 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance 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
- 239000010409 thin film Substances 0.000 description 1
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Images
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
Abstract
The invention provides a preparation method of a Cu-based nano black silicon texturing additive. The preparation method comprises the following steps: 1) dissolving a copper compound in an ethanol solution, adding a reducing agent and a dispersing agent, and stirring and dispersing; 2) adding a silane coupling agent for reaction; 3) filtering, washing, drying, crushing, grinding and sieving to obtain nano copper particles; 4) and mixing the obtained nano copper particles with ethanol, a reducing agent and ammonia water, and adding deionized water for complementing to obtain the nano texturing additive. The invention uses the nano Cu particles as the main raw material of the metal-assisted catalytic black silicon texturing additive, can greatly reduce the material cost when used for black silicon texturing, simultaneously has good texturing effect, and has small scale of the formed textured surface, good uniformity and no color difference.
Description
Technical Field
The invention relates to the field of solar cell manufacturing, in particular to a preparation method of a Cu-based nano black silicon texturing additive.
Background
Black silicon (black silicon) refers to a silicon surface or a silicon-based thin film which can absorb almost all visible light and has extremely low reflectivity, and is a novel semiconductor material which is discovered by recent research and can greatly improve photoelectric conversion efficiency. Compared with the common silicon material, the black silicon material can trap almost all visible light, so the appearance looks black; and the surface structure of the silicon body is an ordered conical microstructure, photons cannot be directly reflected out after entering the structure, but enter the silicon body after being reflected for multiple times, so that the light reflection is reduced, and the light utilization rate is improved. The black silicon material has excellent anti-reflection characteristics, so the black silicon material has an important application prospect in the photovoltaic field.
In the cost of the photovoltaic module, the cost of the silicon wafer accounts for more than 50%, and the cost of the silicon wafer is significant for reducing the overall cost of the photovoltaic module, so that the speed of the low-price internet surfing is accelerated. By adopting the diamond wire cutting polycrystal, the cost of the silicon wafer can be effectively reduced by more than 20%, the cost of a photovoltaic product can be reduced, and the photovoltaic flat-price internet surfing can be realized early. However, the diamond wire cut crystal silicon wafer has small mechanical damage, cannot form an effective suede nucleation center, has poor effect after the traditional acid texturing method, and has high reflectivity and uneven color of the silicon wafer, thereby influencing the generated energy of the assembly. Therefore, the nano texturing additive is required to be adopted and applied to the texturing process of the crystal silicon wafer to form a nano black silicon textured surface, the textured surface is uniform, the process is controllable, and the reflectivity is low. Meanwhile, the problems of diffusion, film coating, silk-screen printing and the like are solved by integrally matching and adjusting the battery process, and the battery efficiency is improved.
The texturing additive is added in the texturing process of the monocrystalline silicon solar cell, and is beneficial to the reaction result and the product performance. The black silicon texturing nano additive mainly utilizes the metal catalysis effect, and Ag obtains electrons from the valence band of silicon at the condition that the energy of an Ag/Si system is far lower than that of the valence band edge of the silicon, so that the Ag is reduced.
Ag++e- VB→Ago(S)
Si+2H2O→SiO2+4H++4e-
H2O2The silicon under the Ag particles is continuously oxidized to accelerate the reaction, and meanwhile, the silicon dioxide is corroded and dissolved by hydrofluoric acid.
2H2O2+Si→SiO2+2H2O
SiO2+6HF→H2SiF6+2H2O
However, the existing black silicon texturing nano additive mostly uses Ag as a main raw material of a metal auxiliary catalytic texturing additive, so that the cost of the existing texturing additive is high.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a Cu (copper) -based black silicon texturing additive, which uses nano Cu particles as a main raw material of the black silicon texturing additive under the metal-assisted catalysis, reduces the material cost, has good texturing effect, and has small scale of the formed textured surface, good uniformity and no color difference.
In order to realize the technical purpose, the technical scheme of the invention is as follows: a preparation method of a Cu-based nano black silicon texturing additive comprises the following steps:
1) dissolving a copper compound in an ethanol solution, adding a reducing agent and a dispersing agent, and stirring and dispersing;
2) adding a silane coupling agent for reaction;
according to the weight percentage, the copper compound, the reducing agent, the dispersing agent and the silane coupling agent account for 10-20%, 0.5-10%, 10-50%, 0.1-1% and the balance of ethanol;
3) filtering, washing, drying, crushing, grinding and sieving to obtain nano copper particles;
4) mixing the obtained nano copper particles with ethanol, a reducing agent and ammonia water to obtain a nano texturing additive;
the weight percentage of the nano copper particles, the ethanol, the reducing agent and the ammonia water is respectively 5-20%, 1-3%, 10-20%, and the balance is deionized water.
Preferably, the copper compound comprises one or more of copper chloride, copper sulfate and copper nitrate. However, the copper compound is not limited to the above.
Preferably, the reducing agent comprises vitamin C, citric acid and glucose.
Preferably, the dispersant comprises PVP, a polyol, oleic acid, an aromatic alcohol ester. The dispersant also has the function of a protective agent, and the protective agent (dispersant) is adsorbed on the surface of the nano copper particles to prevent oxidation chemical reaction and prevent the nano particles from agglomerating.
Preferably, the silane coupling agent comprises gamma-chloropropyltrimethoxysilane, vinyltriethoxysilane and trimethoxysilane.
Preferably, the silane coupling agent is dissolved in an ethanol solution.
Preferably, the stirring and dispersing in the step 1) are carried out by stirring at a high speed for 20-40 minutes by a normal-temperature magnetic rod and dispersing for 5-20 minutes by ultrasonic assistance.
Preferably, the reaction condition of the step 2) is constant temperature and high speed stirring at 60-100 ℃ for 3-5 hours.
Preferably, the drying in step 3) is performed at 80-120 ℃ for 6-10 hours.
Preferably, the selected nano-copper particles are selected from nano-copper particles with the diameter of 20-100 nm.
The preparation method specifically comprises the following steps:
1) adding 10-20 wt% of copper compound into ethanol solution, adding 0.5-10 wt% of reducing agent, adding 10-50 wt% of dispersing agent, stirring at high speed for 20-40 min with normal temperature magnetic bar, and dispersing for 5-20 min with ultrasonic assistance;
2) dripping 0.1-1% of ethanol solution of silane coupling agent, and stirring at a constant temperature of 60-100 ℃ for 3-5 hours at a high speed;
3) filtering, washing with anhydrous ethanol, centrifuging, drying at 80-120 deg.C for 6-10 hr, pulverizing, grinding, sieving, and selecting nanometer copper particles with diameter of 20-100 nm;
4) mixing 5-20 wt% of the nano copper particles, 5-20 wt% of ethanol, 1-3 wt% of reducing agent and 10-20 wt% of ammonia water to prepare a mixed solution, supplementing the mixed solution to 100% by using deionized water, and uniformly stirring and mixing to obtain the nano texturing additive.
In the preparation process of the nano-copper particles, factors such as small and uniform particle size, good water solubility, good dispersibility, difficult oxidation and the like need to be considered, so the surface modification material is added in the preparation process of the nano-copper particles, the macro-phase separation of the nano-particles is prevented, the micro-aggregation of the nano-particles is prevented, and the water solubility and the dispersibility of the nano-particles are increased.
The prepared modified nano-copper particles are added into a chemical solution with a certain formula to form the black silicon texturing additive, so that the nano-copper particles can be uniformly dispersed and have good solubility, and the nano-copper particles can be prevented from being oxidized.
In the black silicon texturing additive, ethanol and reducing agents (vitamin C, citric acid and glucose) play a role in preventing nano copper from being oxidized, and meanwhile, the reducing agents can decompose large-particle nano copper and improve the uniformity of nano copper particles. The ammonia water can increase the solubility of the nano copper particles, improve the adhesion effect of the additive and is beneficial to forming a uniform and porous suede structure.
The texturing additive provided by the invention aims at a black silicon texturing method, Cu is used as a metal catalyst, the Cu does not participate in reaction, and the reaction is accelerated in a place with nano-copper particles, so that a hole structure is formed, and the reflectivity is reduced.
The invention has the beneficial effects that:
1. the nano Cu particles are used as main raw materials of the black silicon texturing additive under metal-assisted catalysis, so that the material cost is greatly reduced, the texturing cost is reduced, and the development of the photovoltaic industry is facilitated.
2. The texturing additive is applied to texturing the surface of a silicon wafer, and the formed textured surface has small size, good uniformity and no color difference.
The invention aims at a black silicon texturing method, takes Cu as a metal catalyst, and aims at diamond wire cutting of a silicon wafer, the reaction is accelerated at a place with nano copper particles, so that a hole structure is formed, the reflectivity is reduced, the size of the formed textured surface is small, the uniformity is good, and no color difference exists. Because copper replaces silver as the main raw material of the metal-assisted catalytic texturing additive, the material cost is greatly reduced, and the development of the photovoltaic industry is facilitated.
Drawings
FIG. 1 is a micro-topography of the application texturing of example 1.
FIG. 2 is an SEM image of texturing applied in example 1.
FIG. 3 is an SEM image of texturing applied in example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a Cu-based nano black silicon texturing additive, which comprises the following steps: 1) dissolving a copper compound in an ethanol solution, adding a reducing agent and a dispersing agent, and stirring and dispersing;
2) adding a silane coupling agent for reaction;
according to the weight percentage, the copper compound, the reducing agent, the dispersing agent and the silane coupling agent account for 10-20%, 0.5-10%, 10-50%, 0.1-1% and the balance of ethanol;
more preferably, the copper compound, the reducing agent, the dispersing agent and the silane coupling agent account for 15%, 5%, 20% and 0.5% by weight, and the balance is ethanol;
3) filtering, washing, drying, crushing, grinding and sieving to obtain nano copper particles;
4) mixing the obtained nano copper particles with ethanol, a reducing agent and ammonia water to obtain a nano texturing additive;
according to the weight percentage, the nano copper particles, the ethanol, the reducing agent and the ammonia water are 5-20%, 1-3% and 10-20% respectively, and the balance is deionized water;
more preferably, the ratio of the nano-copper particles, the ethanol, the reducing agent and the ammonia water is 15%, 20%, 1% and 20% respectively, and the balance is deionized water.
Preferably, the copper compound comprises one or more of copper chloride, copper sulfate and copper nitrate. However, the copper compound is not limited to the above.
Preferably, the reducing agent comprises vitamin C, citric acid and glucose.
Preferably, the dispersant comprises PVP, a polyol, oleic acid, an aromatic alcohol ester.
Preferably, the silane coupling agent comprises gamma-chloropropyltrimethoxysilane, vinyltriethoxysilane and trimethoxysilane.
Preferably, the silane coupling agent is dissolved in an ethanol solution.
Preferably, the stirring and dispersing in the step 1) are carried out by stirring at a high speed for 20-40 minutes by a normal-temperature magnetic rod and dispersing for 5-20 minutes by ultrasonic assistance.
Preferably, the reaction condition of the step 2) is constant temperature and high speed stirring at 60-100 ℃ for 3-5 hours.
Preferably, the drying in step 3) is performed at 80-120 ℃ for 6-10 hours.
Preferably, the selected nano-copper particles are selected from nano-copper particles with the diameter of 20-100 nm.
Specifically, the preparation method comprises the following steps:
1) adding 10-20 wt% of copper compound into ethanol solution, adding 0.5-10 wt% of reducing agent, adding 10-50 wt% of dispersing agent, stirring at high speed for 20-40 min with normal temperature magnetic bar, and dispersing for 5-20 min with ultrasonic assistance;
2) dripping 0.1-1% of ethanol solution of silane coupling agent, and stirring at a constant temperature of 60-100 ℃ for 3-5 hours at a high speed;
3) filtering, washing with anhydrous ethanol, centrifuging, drying at 80-120 deg.C for 6-10 hr, pulverizing, grinding, sieving, and selecting nanometer copper particles with diameter of 20-100 nm;
4) mixing 5-20 wt% of the nano copper particles, 5-20 wt% of ethanol, 1-3 wt% of reducing agent and 10-20 wt% of ammonia water to prepare a mixed solution, supplementing deionized water to 100%, and stirring and mixing uniformly to obtain the nano texturing additive.
Example 1
1. 15 percent of CuCl by weight2Dissolving in appropriate amount of ethanol, adding citric acid 5 wt%, and adding 20% PVP (polyvinylpyrrolidone); stirring the mixture for 30 minutes at a high speed by a magnetic bar at normal temperature, and dispersing the mixture for 15 minutes under the assistance of ultrasonic;
2. 0.5 percent of silane coupling agent dissolved in ethanol is dripped to complement the ethanol to 100 percent, and the mixture is stirred at a constant temperature of 80 ℃ for 4 hours at a high speed;
3. filtering the reaction system, washing with absolute ethyl alcohol, centrifuging, drying at 100 ℃ for 6 hours, crushing, grinding, sieving, and selecting nano copper particles with the diameter of 20-100 nm;
4. preparing a mixed solution from 15% of the Cu nanoparticles, 20% of ethanol, 1% of citric acid and 20% of ammonia water according to the weight percentage, supplementing deionized water to 100%, and stirring and mixing uniformly to obtain the Cu-based black silicon texturing additive.
The Cu-based nano black silicon texturing additive prepared by the method is used for texturing, and the main texturing process comprises ultrasonic cleaning (degreasing and metal ions) of diamond wire cut silicon wafers, cleaning with deionized water → 25% NaOH solution at 85 ℃ for 5min (removing surface damage layers) → deionized water cleaning → aqueous solution prepared from the texturing additive, HF (49%) and deionized water according to the volume ratio of 1: 20-50: 100, preparing aqueous solution from the Cu-based nano black silicon texturing additive, HF (49%) and the deionized water at 6-20 ℃, 1-10min (black silicon texturing) → 5-40% HNO3 (69%) + 10-50% HF (49%) aqueous solution, cleaning with deionized water at 6-30 ℃, 30-300s (hole expansion) → deionized water cleaning → HCl solution (removing metal ions) → 5% diluted NaOH cleaning → deionized water cleaning.
The nano texturing additive is applied to the preparation of the black silicon battery piece to obtain a black silicon texturing surface with the reflectivity of 15%, and as shown in figures 1 and 2, the texturing surface has small scale, good uniformity and no color difference.
Example 2
1. Mixing 10 wt% of CuSO4Adding the mixture into an ethanol solution, adding 0.5 percent by weight of citric acid, and then adding 40 percent of PVP; stirring the mixture for 30 minutes at a high speed by a magnetic bar at normal temperature, and dispersing the mixture for 15 minutes under the assistance of ultrasonic;
2. dripping 1.0% of silane coupling agent dissolved in ethanol, complementing the ethanol to 100%, and stirring at a constant temperature of 60 ℃ for 4 hours at a high speed;
3. filtering, washing with anhydrous ethanol, centrifuging, drying at 80 deg.C for 6 hr, pulverizing, grinding, sieving, and selecting nanometer copper particles with diameter of 30-70 nm.
4. Mixing 13% of the Cu nanoparticles, 15% of ethanol, 2% of citric acid and 10% of ammonia water according to weight percentage to prepare a mixed solution, supplementing deionized water to 100%, and stirring and mixing uniformly to prepare the nano texturing additive.
The Cu-based nano black silicon texturing additive prepared by the method is used for texturing, and the main texturing process comprises ultrasonic cleaning (oil stain and metal ion removal) of diamond wire cut silicon wafers, cleaning with deionized water → cleaning with 5% of HNO3 (69%) + 25% of HF (49%) aqueous solution for 30s (surface damage layer removal) at 8 ℃ (etching pit removal) → cleaning with deionized water → cleaning with the texturing additive of the invention, cleaning with HF (49%) and deionized water according to the volume ratio of 1: 20-50: 100, preparing aqueous solution with 6-20 ℃, 1-10min (black silicon texturing) → 5-40% of HNO3 (69%) + 10-50% of HF (49%) aqueous solution, cleaning with deionized water → cleaning with HCl solution (metal ion) → 5% of dilute NaOH cleaning → cleaning with deionized water at 6-30 ℃ for 30-300s (hole expansion).
The nano texturing additive is applied to the preparation of the black silicon battery piece to obtain a black silicon texturing surface with the reflectivity of 15%, as shown in figure 3, after an acid corrosion method is adopted to remove damage and simultaneously form corrosion pits, a plurality of 30-50nm light trapping small hole structures are formed in the corrosion pits through the black silicon texturing additive, the size of the texturing surface is small, the uniformity is good, and no color difference exists.
Example 3
1. 20 percent of CuCl by weight2Adding the mixture into an ethanol solution, adding 10 percent by weight of glucose, adding 46 percent by weight of glycol, stirring the mixture for 40 minutes at a high speed by using a normal-temperature magnetic bar, and performing ultrasonic-assisted dispersion for 20 minutes;
2. dripping 1% silane coupling agent dissolved in ethanol, then complementing the ethanol to 100%, stirring at constant temperature of 100 ℃ and high speed for 3 hours;
3. filtering, washing with anhydrous ethanol, centrifuging, drying at 120 deg.C for 6 hr, pulverizing, grinding, sieving, and selecting nanometer copper particles with diameter of 20-60 nm;
4. mixing 5% of the Cu nanoparticles, 15% of ethanol, 3% of citric acid and 20% of ammonia water according to weight percentage to prepare a mixed solution, supplementing deionized water to 100%, and stirring and mixing uniformly to prepare the Cu-based black silicon texturing additive.
Example 4
1. 15 percent of CuCl by weight2Adding the mixture into an ethanol solution, adding citric acid with the weight percentage of 7 percent, and then adding 40 percent of propylene glycol; stirring at high speed for 20 minutes by a magnetic bar at normal temperature, and dispersing for 20 minutes by ultrasonic assistance;
2. dripping 1% of ethanol solution of silane coupling agent, complementing the ethanol to 100%, and stirring at constant temperature of 100 ℃ for 5 hours at high speed;
3. filtering, washing with anhydrous ethanol, centrifuging, drying at 120 deg.C for 6 hr, pulverizing, grinding, sieving, and selecting nanometer copper particles with diameter of 20-100 nm.
4. Mixing 15% of the Cu nanoparticles, 5% of ethanol, 2% of citric acid and 15% of ammonia water according to weight percentage to prepare a mixed solution, supplementing deionized water to 100%, and stirring and mixing uniformly to prepare the Cu-based black silicon texturing additive.
Example 5
1. 15 percent of CuCl by weight2Adding into ethanol solution, adding 10 wt% of fructus Citri LimoniaeAcid, then adding 50% propylene glycol; stirring at high speed for 20 minutes by a magnetic bar at normal temperature, and dispersing for 20 minutes by ultrasonic assistance;
2. dripping 1% of ethanol solution of silane coupling agent, complementing the ethanol to 100%, and stirring at constant temperature of 100 ℃ for 5 hours at high speed;
3. filtering, washing with anhydrous ethanol, centrifuging, drying at 120 deg.C for 6 hr, pulverizing, grinding, sieving, and selecting 30-80nm diameter nanometer copper particles.
4. Mixing 10% of the Cu nanoparticles, 20% of ethanol, 1% of citric acid and 10% of ammonia water according to weight percentage to prepare a mixed solution, supplementing deionized water to 100%, and stirring and mixing uniformly to prepare the Cu-based black silicon texturing additive.
The silicon wafer prepared in examples 1 to 4 was tested, and the parameters are shown in Table 1.
TABLE 1 Performance parameters of the silicon wafers prepared in the examples
As can be seen from Table 1, the silicon wafer prepared by the method has excellent conversion efficiency (Eta), open-circuit voltage (Uoc), short-circuit current (Isc) and Filling Factor (FF), has the quality not lower than that of the silicon wafer prepared by the Ag-based nano black silicon texturing additive, and can successfully replace the Ag-based nano black silicon texturing additive.
According to the invention, the nano Cu particles are used as main raw materials of the metal-assisted catalytic black silicon texturing additive, so that the material cost is greatly reduced, the texturing effect is good, the size of the formed textured surface is small, the uniformity is good, no color difference exists, and the quality of the prepared silicon wafer is good.
It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (4)
1. A preparation method of a Cu-based nano black silicon texturing additive is characterized by comprising the following steps:
1) dissolving a copper compound in an ethanol solution, adding a reducing agent and a dispersing agent, and stirring and dispersing;
2) adding a silane coupling agent for reaction;
according to the weight percentage, the copper compound, the reducing agent, the dispersing agent and the silane coupling agent account for 10-20%, 0.5-10%, 10-50%, 0.1-1% and the balance of ethanol;
3) filtering, washing, drying, crushing, grinding and sieving to obtain nano copper particles;
4) mixing 5-20% of the nano copper particles, 5-20% of ethanol, 1-3% of reducing agent and 10-20% of ammonia water according to weight percentage to prepare a mixed solution, supplementing the mixed solution to 100% by using deionized water, and stirring and mixing uniformly to prepare the nano texturing additive;
the copper compound is one or more of copper chloride, copper sulfate and copper nitrate;
the reducing agent is selected from vitamin C, citric acid and glucose;
the dispersing agent is selected from PVP, polyalcohol, oleic acid and aromatic alcohol ester;
the silane coupling agent is selected from gamma-chloropropyltrimethoxysilane, vinyl triethoxysilane and trimethoxysilane;
the reaction condition of the step 2) is that the mixture is stirred at a constant temperature of 60-100 ℃ for 3-5 hours at a high speed.
2. The method for preparing the Cu-based nano black silicon texturing additive according to claim 1, wherein the stirring and dispersing in the step 1) are high-speed stirring by a normal-temperature magnetic rod for 20-40 minutes and ultrasonic-assisted dispersing for 5-20 minutes.
3. The method for preparing the Cu-based nano black silicon texturing additive according to claim 1, wherein the drying of the step 3) is drying at 80-120 ℃ for 6-10 hours.
4. The method of claim 1, wherein the selected nano-copper particles are selected to be nano-copper particles with a diameter of 20-100 nm.
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