CN113964215B - Texturing method of TOPcon battery - Google Patents
Texturing method of TOPcon battery Download PDFInfo
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- CN113964215B CN113964215B CN202111584072.1A CN202111584072A CN113964215B CN 113964215 B CN113964215 B CN 113964215B CN 202111584072 A CN202111584072 A CN 202111584072A CN 113964215 B CN113964215 B CN 113964215B
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 43
- 239000004094 surface-active agent Substances 0.000 claims abstract description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 36
- 239000010703 silicon Substances 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 33
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- 239000003513 alkali Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 14
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 11
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 11
- -1 amino beta-cyclodextrin Chemical compound 0.000 claims abstract description 11
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- 229960004853 betadex Drugs 0.000 claims abstract description 11
- 239000000832 lactitol Substances 0.000 claims abstract description 11
- VQHSOMBJVWLPSR-JVCRWLNRSA-N lactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-JVCRWLNRSA-N 0.000 claims abstract description 11
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- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
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- 229940072106 hydroxystearate Drugs 0.000 claims description 28
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 17
- LSYBWANTZYUTGJ-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCO LSYBWANTZYUTGJ-UHFFFAOYSA-N 0.000 claims description 10
- LDCYZAJDBXYCGN-VIFPVBQESA-N 5-hydroxy-L-tryptophan Chemical compound C1=C(O)C=C2C(C[C@H](N)C(O)=O)=CNC2=C1 LDCYZAJDBXYCGN-VIFPVBQESA-N 0.000 claims description 10
- 229940077481 dl- 5-hydroxytryptophan Drugs 0.000 claims description 10
- FWDLHTBMGQEUDU-UHFFFAOYSA-M sodium;2-hydroxy-2-phenylacetate Chemical compound [Na+].[O-]C(=O)C(O)C1=CC=CC=C1 FWDLHTBMGQEUDU-UHFFFAOYSA-M 0.000 claims description 10
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 238000002310 reflectometry Methods 0.000 abstract description 16
- 230000007547 defect Effects 0.000 abstract description 5
- 235000012431 wafers Nutrition 0.000 description 29
- 230000000694 effects Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 17
- 239000003093 cationic surfactant Substances 0.000 description 14
- HBGOLJKPSFNJSD-UHFFFAOYSA-N Etamsylate Chemical compound CC[NH2+]CC.OC1=CC=C(O)C(S([O-])(=O)=O)=C1 HBGOLJKPSFNJSD-UHFFFAOYSA-N 0.000 description 13
- 229960004817 etamsylate Drugs 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 description 9
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 229920005591 polysilicon Polymers 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 101710138657 Neurotoxin Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002581 neurotoxin Substances 0.000 description 1
- 231100000618 neurotoxin Toxicity 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- 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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
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- 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
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Abstract
The invention discloses a texturing method of a TOPcon battery, which relates to the technical field of solar batteries and specifically comprises the following steps: pretreating the surface of the silicon wafer to remove organic dirt on the surface; preparing a texturing additive; texturing, namely mixing a texturing additive and alkali liquor to obtain texturing liquid, and immersing the texturing liquid into the silicon wafer subjected to surface pretreatment for surface texturing; wherein, the raw materials of the texturing additive comprise: quaternary ammonium salt surfactant, polyvinylpyrrolidone, lactitol, total amino beta-cyclodextrin and deionized water. The texture structure formed by the texturing method of the TOPcon battery provided by the invention is more regular, the reflectivity is obviously reduced, the defects of the battery structure can be effectively overcome, the short-circuit current of the battery is improved, the maximum power is increased, and the photoelectric conversion efficiency is enhanced.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a texturing method of a TOPcon cell.
Background
In order to improve the efficiency of the battery, various battery structures are developed, such as PERC, HIT, IBC, TOPCon, and the like, wherein the TOPCon battery structure is to prepare an ultra-thin silicon oxide layer and a highly doped polysilicon layer on the silicon surface, the minority carrier recombination rate on the silicon surface can be significantly reduced by utilizing the chemical passivation of the silicon oxide and the field passivation of the polysilicon layer, and the highly doped polysilicon layer can significantly improve the conductivity of majority carriers, which is beneficial to improving the open-circuit voltage and the filling factor of the battery. Compared with a P-type solar cell, the N-type cell has the advantages of good metal impurity pollution resistance due to light attenuation, long minority carrier diffusion length and the like, and is widely applied.
In the preparation process of the TOPCon structure battery, a layer of polycrystalline silicon is required to be plated on the back surface of a silicon wafer, but the winding plating phenomenon is generated in the step, the polycrystalline silicon is also plated on the edge of the front surface of the silicon wafer, the appearance and the efficiency are influenced, and the finished product is degraded. For removing the polysilicon by-pass plating, there are three main solutions in the industry: firstly, polycrystalline silicon coated around the front surface of a silicon wafer is removed by hydrofluoric acid and nitric acid, and the method has a narrow process window, so that PN junctions on the front surface are easily damaged, and the yield of products is greatly reduced; secondly, the polycrystalline silicon coated on the front side of the silicon wafer is removed only by adopting inorganic alkali (potassium hydroxide or sodium hydroxide), the process window of the method is narrow, the yield is not high during mass production, the efficiency and yield fluctuation are large, and the boron expansion capacity and the battery efficiency are low due to the thick BSG; and thirdly, removing the polysilicon coated around the front surface of the silicon wafer by adopting tetramethyl ammonium hydroxide, wherein the tetramethyl ammonium hydroxide used in the method belongs to neurotoxin and has certain damage to human bodies.
Disclosure of Invention
The invention aims to provide a texturing method of a TOPcon battery, wherein a textured structure formed by the texturing method is more regular, the reflectivity is obviously reduced, the defects of the battery structure can be effectively overcome, the short-circuit current of the battery is improved, the maximum power is increased, and the photoelectric conversion efficiency is enhanced.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a texturing method of a TOPcon battery comprises the following steps:
(1) pretreating the surface of the silicon wafer to remove organic dirt on the surface;
(2) preparing a texturing additive;
(3) texturing, namely mixing a texturing additive and alkali liquor to obtain texturing liquid, and immersing the texturing liquid into the silicon wafer subjected to surface pretreatment for surface texturing;
wherein, the raw materials of the texturing additive comprise: quaternary ammonium salt surfactant, polyvinylpyrrolidone, lactitol, total amino beta-cyclodextrin and deionized water. According to the invention, the texturing additive is added into the texturing alkali liquor, and the additive contains a surfactant, so that the surface tension of water can be reduced, and further, silicon wafers can be effectively wetted; and the additive can replace isopropanol, is nontoxic and noncorrosive, further reduces pollution and saves cost. Wherein, lactitol and other organic matters increase nucleation starting points of inverted pyramid structures on the silicon surface, and the formed inverted pyramids are uniform and fine; meanwhile, the use temperature of the wool making alkali liquor is lower, and the reaction time is shortened. The light trapping effect of the solar cell can be effectively improved by utilizing the permeability and the surface activity of the water-soluble organic substance, so that the photoelectric conversion efficiency of the solar cell is remarkably improved. The texturing additive has simple manufacturing and using processes, low equipment cost and good repeatability.
According to some embodiments, the lye comprises an aqueous solution of an organic base and an inorganic base.
According to some embodiments, the organic base comprises tetramethylguanidine; the inorganic base comprises potassium hydroxide or sodium hydroxide.
According to some embodiments, the quaternary ammonium salt surfactant comprises dodecyl trimethyl ammonium bromide.
According to some embodiments, the texturing conditions include a texturing temperature of 80-85 ℃ and a texturing time of 10-20 min.
According to some embodiments, the quaternary ammonium salt type surfactant is replaced by a novel quaternary ammonium salt type surfactant; the novel quaternary ammonium salt surfactant is synthesized by a two-step method by taking lupeol-beta-hydroxystearate, thionyl chloride and N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine as raw materials. The novel quaternary ammonium salt surfactant prepared by the invention has higher activity of reducing surface tension, and is compounded with polyvinylpyrrolidone for use, so that the effect of reducing the surface tension of water and wetting a silicon wafer is better, and the silicon wafer after texture making is obtained, and compared with the conventional pyramid texture, the inverted pyramid texture has lower reflectivity. The lactitol and the total amino beta-cyclodextrin in the additive can be selectively adsorbed on the BSG to form a protective layer, so that the diffusion rate of the alkali liquor is effectively reduced, the alkali liquor is prevented from reacting with the BSG, the corrosion of alkali to a phosphorus diffusion part and a boron diffusion part is reduced or avoided, the stability of mass production is ensured, the performance of the prepared battery is obviously improved, and the maximum power and the photoelectric conversion performance of the battery are obviously improved.
According to some embodiments, the method of preparing the novel quaternary ammonium salt surfactant specifically comprises:
chlorinating the lupeol-beta-hydroxystearate with thionyl chloride to obtain chlorinated lupeol-beta-hydroxystearate;
taking chlorinated lupeol-beta-hydroxystearate to react with N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine to obtain the novel quaternary ammonium salt surfactant.
Specifically, the preparation method of the novel quaternary ammonium salt surfactant comprises the following steps:
mixing lupeol-beta-hydroxystearate and pyridine, and slowly dripping thionyl chloride at the temperature of 10-20 ℃; after the dropwise addition is finished, raising the temperature of the system to 70-80 ℃, stirring and carrying out reflux reaction for 10-12 h; then adding 15-18 wt% sodium hydroxide or potassium hydroxide to adjust the pH of the upper layer of the reaction mixture to 7-8, retaining the upper layer liquid, washing with hot deionized water for 8-10 times, and performing vacuum drying to obtain chlorinated lupeol-beta-hydroxystearate;
dissolving chlorinated lupeol-beta-hydroxystearate in ethanol, slowly adding N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine, and then stirring and refluxing at 80-90 ℃ for 48-54 h; and (3) removing ethanol by rotary evaporation, taking the lower layer precipitate, adding dichloromethane, and filtering to obtain the novel quaternary ammonium salt surfactant.
According to some embodiments, the mass ratio of lupeol-beta-hydroxystearate to pyridine is 1: 0.3 to 0.6; the mass ratio of the thionyl chloride to the lupeol-beta-hydroxystearate is 0.4-0.7: 1.
according to some embodiments, the solid to liquid ratio of chlorinated lupeol-beta-hydroxystearate to ethanol is 1.8 to 2.5 g/mL; the mass ratio of the N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine to the chlorinated lupeol-beta-hydroxystearate is 0.1-0.25: 1.
specifically, the texturing method of the TOPcon battery specifically comprises the following steps:
cutting a silicon wafer into small pieces by using a laser scribing machine, performing ultrasonic treatment for 10-15 min by using alcohol and acetone respectively, and then washing 3-5 times by using deionized water;
mixing quaternary ammonium salt surfactant, polyvinylpyrrolidone, lactitol, total amino beta-cyclodextrin and deionized water to prepare a texturing additive;
taking alkali liquor, adding a texturing additive to obtain a texturing solution, and reacting for 10-20 min at the water bath temperature of 80-85 ℃; and (3) after the reaction is finished, performing ultrasonic treatment on the sample for 15-20 min by using deionized water, and then drying by using nitrogen.
According to some embodiments, the quaternary ammonium salt cationic surfactant, the polyvinylpyrrolidone, the lactitol, and the total amino β -cyclodextrin are present in a mass ratio of 1: 0.05-0.2: 0.2-0.4: 0.02 to 0.05; the mass ratio of the quaternary ammonium salt cationic surfactant to the deionized water is 1: 0.5 to 1.
More preferably, the texturing additive further comprises sodium mandelate and DL-5-hydroxytryptophan; wherein the mass ratio of sodium mandelate to quaternary ammonium salt cationic surfactant is 0.1-0.3: 1; the mass ratio of DL-5-hydroxytryptophan to quaternary ammonium salt cationic surfactant is 0.1-0.2: 1. sodium mandelate and DL-5-hydroxytryptophan are added into the texturing additive and are compounded with other components, so that the reflectivity is obviously reduced, probably because the addition of the substance can enable the texture structure formed after texturing to be more uniform; meanwhile, the performance of the battery can be obviously improved, the short-circuit current is increased, the maximum power is improved, the photoelectric conversion efficiency is enhanced, and the supposition is that the battery can be compounded with total amino beta-cyclodextrin and the like to form a more uniform and compact network structure, and the battery is adsorbed on BSG to form a protective layer, so that the protection effect is better, and the internal structure of the textured surface after texturing is more uniform.
Preferably, the alkali liquor is sodium hydroxide or strong potassium oxide solution containing tetramethylguanidine; wherein the concentration of the sodium hydroxide or potassium hydroxide solution is 0.01-0.03 g/mL; the usage amount of the tetramethylguanidine is 0.01-0.02 g/mL; the mass ratio of the texturing additive to the sodium hydroxide or potassium hydroxide solution is 0.2-2: 100.
more preferably, the alkali liquor is also added with etamsylate; wherein the adding amount of the etamsylate is 0.005-0.01 g/mL. According to the invention, the etamsylate is added into the alkali liquor, so that the alkali can be gained, and the dosage of the etamsylate is reduced; the reaction is more uniform, a more uniform small pyramid structure is formed inside the textured microstructure after texturing, the reflectivity of the crystalline silicon is effectively reduced, the short-circuit current of the battery is obviously improved, and the aim of improving the efficiency is further fulfilled; meanwhile, the non-uniformity of light absorption of the cell can be reduced, and the photoelectric conversion efficiency of the cell is improved.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the texturing additive is added into the texturing alkali liquor, and the novel quaternary ammonium salt surfactant in the additive has higher activity of reducing surface tension, so that the silicon wafer after texturing is obtained and has lower reflectivity. The performance of the prepared battery is obviously improved, and the maximum power and the photoelectric conversion efficiency of the battery are obviously improved. Sodium mandelate and DL-5-hydroxytryptophan are also added into the texturing additive and are compounded with other components, so that the reflectivity is obviously reduced, and the performance of the battery can be obviously improved. In addition, the etamsylate is added into the alkali liquor, so that the using amount of the alkali can be effectively reduced; and the reaction is more uniform, the reflectivity of the crystalline silicon is effectively reduced, and the short-circuit current and the photoelectric conversion efficiency of the battery are obviously improved.
Therefore, the invention provides a texturing method of the TOPcon battery, the textured structure formed by the texturing method is more regular, the reflectivity is obviously reduced, the defects of the battery structure can be effectively overcome, the short-circuit current of the battery is improved, the maximum power is increased, and the photoelectric conversion efficiency is enhanced.
Drawings
FIG. 1 shows the results of IR spectroscopy of a novel quaternary ammonium surfactant of test example 1 of the present invention;
FIG. 2 shows SEM test results in test example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
the preparation method of the novel quaternary ammonium surfactant comprises the following steps:
according to the mass ratio of 1: 0.42 mixing lupeol-beta-hydroxystearate and pyridine, and slowly dripping thionyl chloride (with lupeol-beta-hydroxystearate at a mass ratio of 0.55: 1) at 15 deg.C; after the dropwise addition is finished, the temperature of the system is raised to 75 ℃, and the stirring reflux reaction is carried out for 12 hours; then adding 16.5wt% sodium hydroxide to adjust the pH of the upper layer of the reaction mixture to 7.5, retaining the upper layer liquid, washing with hot deionized water for 8 times, and vacuum drying to obtain chlorinated lupeol-beta-hydroxystearate;
dissolving chlorinated lupeol-beta-hydroxystearate in ethanol at a solid-to-liquid ratio of 2.1 g/mL; slowly adding N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine (the mass ratio of the N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine to the chlorinated lupeol-beta-hydroxystearate is 0.18: 1), and then stirring and refluxing for reaction for 48 hours at the temperature of 88 ℃; and (3) removing ethanol by rotary evaporation, taking the lower layer precipitate, adding dichloromethane, and filtering to obtain the novel quaternary ammonium salt surfactant.
A texturing method of a TOPcon battery comprises the following steps:
cutting a silicon wafer into 40 × 40mm pieces by using a laser scribing machine, performing ultrasonic treatment for 10min by using alcohol and acetone respectively, and then washing with deionized water for 5 times;
according to the mass ratio of 1: 0.12: 0.3: 0.036, mixing the novel quaternary ammonium salt type cationic surfactant, polyvinylpyrrolidone, lactitol and total amino beta-cyclodextrin, and adding deionized water (the mass ratio of the novel quaternary ammonium salt type cationic surfactant to the deionized water is 1: 0.8) to prepare the wool making additive; taking a sodium hydroxide solution containing tetramethylguanidine (the usage amount is 0.015 g/mL) and having the concentration of 0.015g/mL, adding a texturing additive (the mass ratio of the texturing additive to the sodium hydroxide solution is 1.1: 100) to obtain a texturing solution, and reacting for 15min at the water bath temperature of 82 ℃; and (3) after the reaction is finished, performing ultrasonic treatment on the sample for 15min by using deionized water, and then drying the sample by using nitrogen.
Example 2:
a difference from example 1 in the preparation of a novel quaternary ammonium surfactant: the mass ratio of lupeol-beta-hydroxystearate to pyridine is 1: 0.32 of; the mass ratio of the thionyl chloride to the lupeol-beta-hydroxystearate is 0.45; the mass ratio of the N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine to the chlorinated lupeol-beta-hydroxystearate is 0.14: 1.
the difference between the texturing method of the TOPcon battery and the embodiment 1 is that:
the novel quaternary ammonium surfactant was prepared in this example;
the mass ratio of the novel quaternary ammonium salt cationic surfactant to the polyvinylpyrrolidone to the lactitol to the total amino beta-cyclodextrin is 1: 0.08: 0.24: 0.04; the mass ratio of the novel quaternary ammonium salt cationic surfactant to the deionized water is 1: 0.6;
the concentration of the sodium hydroxide solution is 0.01 g/mL; the usage amount of the tetramethylguanidine is 0.016 g/mL; the mass ratio of the texturing additive to the sodium hydroxide solution is 0.8: 100.
example 3:
a difference from example 1 in the preparation of a novel quaternary ammonium surfactant: the mass ratio of lupeol-beta-hydroxystearate to pyridine is 1: 0.56; the mass ratio of the thionyl chloride to the lupeol-beta-hydroxystearate is 0.6; the mass ratio of the N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine to the chlorinated lupeol-beta-hydroxystearate is 0.22: 1.
the difference between the texturing method of the TOPcon battery and the embodiment 1 is that:
the novel quaternary ammonium surfactant was prepared in this example;
the mass ratio of the novel quaternary ammonium salt cationic surfactant to the polyvinylpyrrolidone to the lactitol to the total amino beta-cyclodextrin is 1: 0.16: 0.3: 0.28; the mass ratio of the novel quaternary ammonium salt cationic surfactant to the deionized water is 1: 0.9; potassium hydroxide was used instead of sodium hydroxide.
Example 4:
a novel quaternary ammonium surfactant was prepared as in example 1.
The difference between the texturing method of the TOPcon battery and the embodiment 1 is that: the texturing additive also comprises sodium mandelate and DL-5-hydroxytryptophan acid; wherein the mass ratio of sodium mandelate to quaternary ammonium salt cationic surfactant is 0.2: 1; the mass ratio of DL-5-hydroxytryptophan to quaternary ammonium salt type cationic surfactant is 0.14: 1.
example 5:
the difference between the texturing method of the TOPcon battery and the embodiment 4 is that: dodecyl trimethyl ammonium bromide is adopted to replace a novel quaternary ammonium salt cationic surfactant.
Example 6:
a novel quaternary ammonium surfactant was prepared as in example 1.
The difference between the texturing method of the TOPcon battery and the embodiment 1 is that: adding etamsylate into the alkali liquor; wherein the adding amount of the etamsylate is 0.008 g/mL.
Example 7:
a novel quaternary ammonium surfactant was prepared as in example 4.
The difference between the texturing method of the TOPcon battery and the embodiment 4 is that: adding etamsylate into the alkali liquor; wherein the adding amount of the etamsylate is 0.008 g/mL.
Example 8:
the difference between the texturing method of the TOPcon battery and the embodiment 5 is that: adding etamsylate into the alkali liquor; wherein the adding amount of the etamsylate is 0.008 g/mL.
Example 9:
the difference between the texturing method of the TOPcon battery and the embodiment 8 is that: sodium mandelate and DL-5-hydroxytryptophan are not included in the texturing additive.
Example 10:
the difference between the texturing method of the TOPcon battery and the embodiment 1 is that: dodecyl trimethyl ammonium bromide is adopted to replace a novel quaternary ammonium salt cationic surfactant.
Test example 1:
FT-IR characterization
And testing the sample by using a Fourier infrared transform spectrometer. Preparing a sample by adopting a KBr tabletting method; and (3) placing the sample under an attenuated total reflection accessory, and scanning the surface of the sample to obtain an infrared spectrogram. The test conditions are specifically as follows: the scanning wavelength is 500-4000 cm-1。
The above test was performed on the novel quaternary ammonium salt type surfactant prepared in example 1, and the results are shown in fig. 1. As can be seen from the analysis of the figure, the infrared spectrum of the novel quaternary ammonium salt surfactant prepared in example 1 is 3650-3200 cm-1The characteristic absorption peak of-OH group appears in the range of 3000-2750 cm-1Characteristic absorption peaks of methyl and methylene appear in the range of 1704cm-1Characteristic absorption peak of about C = O bond, 1640cm-1The characteristic absorption peak of C = C bond appears nearby, at 1482cm-1A bending vibration absorption peak of a C-H bond appears nearby; at 1126cm-1A characteristic absorption peak of C-O bond appears nearby; the above results show that the novel quaternary ammonium salt surfactant of example 1 was successfully prepared.
SEM characterization
The surface appearance structure of the sample is observed by a scanning electron microscope.
The above test was performed on the textured silicon wafer prepared in example 1, and the results are shown in fig. 2. Analysis in the figure shows that the whole surface of the silicon wafer covers the suede, and the formed suede has better uniformity.
Determination of surface tension
The test was carried out by using a fully automatic tensiometer (purchased from Shanghai Med digital technical equipment Co., Ltd., model JK 998) and preparing a surfactant aqueous solution having a concentration of 1mmol/L at ordinary temperature and measuring by a ring tension method.
The above test was performed on dodecyl trimethyl ammonium bromide and the novel quaternary ammonium salt surfactant prepared in examples 1 to 3, and a complex group N1 was set: dodecyl trimethyl ammonium bromide and polyvinylpyrrolidone (the mass ratio of the dodecyl trimethyl ammonium bromide to the polyvinylpyrrolidone is 1: 0.1); composite set N2: the above test was carried out with the novel quaternary ammonium salt surfactant prepared in example 1 and polyvinylpyrrolidone (both in a mass ratio of 1: 0.1), and the final results are shown in table 1:
table 1 surface tension test results
| Sample (I) | Surface tension (mN/m) |
| Dodecyl trimethyl ammonium bromide | 80.5 |
| Example 1 | 62.2 |
| Example 2 | 61.8 |
| Example 3 | 62.5 |
| N1 | 51.6 |
| N2 | 22.7 |
From the data analysis in table 1, it can be seen that the surface tension of water after the treatment of the novel quaternary ammonium salt surfactant prepared in example 1 is significantly lower than that of dodecyl trimethyl ammonium bromide, which indicates that the surface tension reducing capability of the novel quaternary ammonium salt surfactant prepared by the present invention is significantly improved. In addition, after the samples in the N2 group are treated, the surface tension reduction rate of water is obviously better than that of the samples in the N1 group, and the fact that the novel quaternary ammonium salt surfactant prepared by the method is used in combination with polyvinylpyrrolidone shows that the effect of reducing the surface tension is better.
Test example 2:
reflectance measurement
And placing the textured silicon wafer sample into a spectrophotometer to test the reflectivity of incident light with the wavelength of 400-1100 nm.
The results of the above tests on the textured silicon wafers obtained in examples 1 to 10 are shown in table 2:
TABLE 2 reflectivity test results
| Sample (I) | Reflectivity/%) |
| Example 1 | 6.1 |
| Example 2 | 6.3 |
| Example 3 | 5.9 |
| Example 4 | 4.2 |
| Example 5 | 7.8 |
| Example 6 | 4.5 |
| Example 7 | 3.1 |
| Example 8 | 7.0 |
| Example 9 | 8.5 |
| Example 10 | 9.4 |
As can be seen from data analysis in table 2, the reflectivity of the silicon wafer subjected to texturing by the texturing method provided in example 1 is significantly lower than that of example 10, which indicates that the novel quaternary ammonium salt surfactant prepared by using lupeol-beta-hydroxystearate as one of the raw materials is used in combination with other components as a texturing additive to act on the silicon wafer, so that the reflectivity of the silicon wafer subjected to texturing can be effectively reduced; the effect of example 4 is better than that of example 1, and the effect of example 5 is better than that of example 10 and that of example 8 is better than that of example 9, which shows that the addition of sodium mandelate and DL-5-hydroxytryptophan in the texturing additive can further reduce the reflectivity of the silicon wafer after texturing. The effect of example 6 is better than that of example 1, the effect of example 7 is better than that of example 4, the effect of example 8 is better than that of example 5, and the effect of example 9 is better than that of example 10, which shows that the addition of the etamsylate in the alkali liquor has an enhanced effect on the reduction of the reflectivity of the silicon wafer after texturing.
Determination of Battery Performance
And respectively carrying out diffusion, edge etching, film coating, printing and rapid sintering on the textured silicon wafer sample to obtain the solar cell. The solar cell is placed at 1000w/m2In the illumination intensity, the short-circuit current, the maximum power and the conversion efficiency of the battery are tested.
The results of the above tests on the textured silicon wafers obtained in examples 1 to 10 are shown in table 3:
TABLE 3 Battery Performance test results
| Sample (I) | Short-circuit current/A | Maximum power/W | Transformation efficiency/% |
| Example 1 | 8.45 | 4.42 | 17.93 |
| Example 2 | 8.50 | 4.47 | 18.01 |
| Example 3 | 8.39 | 4.38 | 17.85 |
| Example 4 | 9.11 | 4.80 | 19.90 |
| Example 5 | 9.07 | 4.29 | 17.42 |
| Example 6 | 8.96 | 5.11 | 20.61 |
| Example 7 | 9.68 | 5.46 | 21.18 |
| Example 8 | 9.59 | 4.58 | 18.27 |
| Example 9 | 8.81 | 4.67 | 18.79 |
| Example 10 | 8.36 | 3.92 | 16.03 |
As can be seen from data analysis in table 3, the maximum power and the conversion effect of the battery prepared from the silicon wafer subjected to the texturing method provided in example 1 are higher than those of example 10, and the short-circuit current is equivalent to that of example 10, which indicates that the novel quaternary ammonium salt surfactant prepared by using lupeol-beta-hydroxystearate as one of the raw materials is used in combination with other components and acts on the silicon wafer as a texturing additive to obviously improve the performance of the battery, and the maximum power and the photoelectric conversion efficiency are significantly enhanced without negatively affecting the short-circuit current. The short-circuit current, the maximum power and the conversion effect of the battery prepared from the silicon wafer subjected to texturing by the texturing method provided in example 4 are better than those of example 1, the effect of example 5 is better than that of example 10, and the effect of example 8 is better than that of example 9, which shows that the addition of sodium mandelate and DL-5-hydroxytryptophan in the texturing additive, the silicon wafer subjected to texturing is regular and uniform, the texture defects are few, the performance of the battery is further improved, and the short-circuit current, the maximum power and the photoelectric conversion efficiency are obviously increased. The effect of example 6 is better than that of example 1, the effect of example 7 is better than that of example 4, the effect of example 8 is better than that of example 5, and the effect of example 9 is better than that of example 10, which shows that the addition of the etamsylate in the alkali solution can further reduce the defects of the texture surface, the texture surface of the textured silicon wafer is more regular, and the performance of the battery is effectively improved.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (6)
1. A texturing method of a TOPcon battery is characterized by comprising the following steps:
(1) pretreating the surface of the silicon wafer to remove organic dirt on the surface;
(2) preparing a texturing additive;
(3) texturing, namely mixing a texturing additive and alkali liquor to obtain texturing liquid, and immersing the texturing liquid into the silicon wafer subjected to surface pretreatment for surface texturing;
wherein, the raw materials of the texturing additive comprise: quaternary ammonium salt surfactant, polyvinylpyrrolidone, lactitol, total amino beta-cyclodextrin and deionized water;
the mass ratio of the quaternary ammonium salt surfactant to the polyvinylpyrrolidone to the lactitol to the total amino beta-cyclodextrin is 1: 0.05-0.2: 0.2-0.4: 0.02 to 0.05;
the quaternary ammonium salt surfactant is synthesized by a two-step method by taking lupeol-beta-hydroxystearate, thionyl chloride and N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine as raw materials;
the preparation method of the quaternary ammonium salt surfactant specifically comprises the following steps:
chlorinating the lupeol-beta-hydroxystearate with thionyl chloride to obtain chlorinated lupeol-beta-hydroxystearate;
and reacting chlorinated lupeol-beta-hydroxystearate with N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine to obtain the quaternary ammonium salt surfactant.
2. The method as claimed in claim 1, wherein the alkaline solution comprises an aqueous solution of an organic base and an inorganic base.
3. The method of claim 2, wherein the organic base comprises tetramethylguanidine; the inorganic base comprises potassium hydroxide or sodium hydroxide.
4. The method as claimed in claim 1, wherein the texturing conditions include a texturing temperature of 80-85 ℃ and a texturing time of 10-20 min.
5. The method as claimed in claim 1, wherein the texturing additive further comprises sodium mandelate and DL-5-hydroxytryptophan.
6. The method of claim 1, wherein etafil is further added to the alkaline solution.
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