CN111040766B - Polycrystalline silicon wafer texturing solution, preparation method of black silicon material and application of black silicon material in accelerating PERC battery LeTID recovery - Google Patents
Polycrystalline silicon wafer texturing solution, preparation method of black silicon material and application of black silicon material in accelerating PERC battery LeTID recovery Download PDFInfo
- Publication number
- CN111040766B CN111040766B CN201911360376.2A CN201911360376A CN111040766B CN 111040766 B CN111040766 B CN 111040766B CN 201911360376 A CN201911360376 A CN 201911360376A CN 111040766 B CN111040766 B CN 111040766B
- Authority
- CN
- China
- Prior art keywords
- polycrystalline silicon
- silicon wafer
- texturing
- silicon material
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 99
- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 79
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000011084 recovery Methods 0.000 title claims abstract description 10
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 title claims abstract 6
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 title claims abstract 6
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 title claims abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 22
- 238000005530 etching Methods 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 17
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 48
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 238000004140 cleaning Methods 0.000 claims description 23
- 229920001145 Poly(N-vinylacetamide) Polymers 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001133 acceleration Effects 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 69
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 33
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 29
- 229910052710 silicon Inorganic materials 0.000 description 23
- 239000010703 silicon Substances 0.000 description 23
- 239000002253 acid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002161 passivation Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229920005591 polysilicon Polymers 0.000 description 6
- 238000002310 reflectometry Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005247 gettering Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- 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
-
- 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
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic System
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a polycrystalline silicon wafer texturing solution, a preparation method of a black silicon material and application of the polycrystalline silicon wafer texturing solution to acceleration of PERC battery LeTID recovery. The polycrystalline silicon wafer texturing liquid comprises: HF. Mn (NO)3)2poly-N-vinylacetamide and water. By adopting the polycrystalline silicon wafer texturing solution, a damage layer does not need to be removed before texturing, the polycrystalline silicon wafer can be directly immersed into the texturing solution for etching, rapid texturing is realized in a mild environment, the etched polycrystalline silicon wafer can be used for preparing a solar cell after being cleaned and impurities are removed, the use is convenient, and the texturing time is short. The invention also provides a preparation method and application of the black silicon material, and the black silicon material has the characteristic of accelerating LeTID recovery when being used in the polycrystalline silicon PERC battery processing technology, can improve the battery generating efficiency, and is beneficial to popularization and application of the polycrystalline silicon PERC battery.
Description
Technical Field
The invention relates to the field of photovoltaic materials, in particular to a preparation method of polycrystalline silicon wafer texturing solution and a black silicon material and application of the polycrystalline silicon wafer texturing solution and the black silicon material in accelerating the LeTID recovery of a PERC battery.
Background
Solar cells, also known as "solar chips" or "photovoltaic cells", are devices that directly convert light energy into electrical energy through the photoelectric effect or the photochemical effect, and crystalline silicon solar cells that work with the photoelectric effect are the mainstream at present. Polycrystalline silicon solar cells are favored because of the advantages of abundant raw materials, low cost, high conversion efficiency, good stability and the like. The polycrystalline silicon wafer is a core component of the polycrystalline silicon solar cell for photoelectric conversion, and in order to improve the photoelectric conversion efficiency of the polycrystalline silicon wafer, a textured surface is usually formed on the surface of the silicon wafer through a texturing process to enhance the light trapping effect of the silicon wafer and reduce light reflection.
For the polycrystalline silicon slice manufactured by the early mortar cutting process, irregular pits exist on the surface of the polycrystalline silicon slice, and an effective suede structure can be formed on the surface of the polycrystalline silicon slice by directly adopting conventional acid texturing. The diamond wire cutting technology is widely applied on the basis of the advantages of high production rate, small mechanical damage, accurate slice thickness control and the like, and gradually replaces mortar cutting to become a mainstream silicon slice cutting mode. However, the surface of a polycrystalline silicon wafer cut by diamond wires is in a mixed shape of a smooth cutting surface and irregular pits, an effective suede structure cannot be formed on the smooth cutting surface by adopting a conventional acid texturing method, in order to solve the problem, a nano structure can be formed on the surface of the polycrystalline silicon wafer by adopting a special texturing process at present, and the silicon wafer prepared by adopting the process is black to the naked eye, so that the silicon wafer is called black silicon. The polycrystalline black silicon texturing process mainly comprises a dry texturing process and a wet texturing process. The wet black silicon texturing process is a Metal Catalyzed Chemical Etching (MCCE) method, wherein Metal is attached to the surface of a silicon wafer, the surface of the silicon wafer is etched by using a mixed solution of hydrofluoric acid and a strong oxidant, and the Metal attached to the surface of the silicon wafer is deposited downwards along with the Etching process, so that a nano structure is formed on the surface of the silicon wafer, and the reflectivity of the surface of the silicon wafer is effectively reduced. However, the method needs to remove the damaged layer on the surface of the silicon wafer formed by diamond wire cutting before the nano structure is prepared, the operation of the whole texturing process is complicated, and meanwhile, the silver nitrate solution required by etching increases the texturing cost and causes environmental pollution, so that the method has certain disadvantages.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of complicated steps, high cost and environmental pollution of a wet black silicon texturing process in the prior art, so that the preparation methods of the polycrystalline silicon wafer texturing solution and the black silicon material and the application of the polycrystalline silicon wafer texturing solution and the black silicon material in accelerating the LETID recovery of the PERC battery are provided.
In a first aspect, the present invention provides a polycrystalline silicon wafer texturing solution, including: HF. Mn (NO)3)2poly-N-vinylacetamide and water.
Furthermore, in the polycrystalline silicon wafer texturing solution, the concentration of HF is 3.63-4.24mol/L, and Mn (NO) is3)2The concentration of (A) is 2.6-3.1 mol/L.
In a second aspect, the invention provides a preparation method of the polycrystalline silicon wafer texturing solution, which comprises the following steps:
the HF, Mn (NO)3)2And mixing the poly N-vinyl acetamide and water to obtain the polycrystalline silicon wafer texturing solution.
Further, the preparation method of the polycrystalline silicon wafer texturing solution comprises the following steps:
the aqueous solution of HF and Mn (NO)3)2The aqueous solution of (2) and the aqueous solution of poly (N-vinylacetamide) are dissolved in water so that the concentration of the HF is 3.63 to 4.24mol/L and the Mn (NO) is3)2The concentration of the N-vinyl acetamide is 2.6-3.1mol/L, and the volume fraction of the aqueous solution of the poly N-vinyl acetamide is 1% -8%.
Further, the preparation method of the polycrystalline silicon wafer texturing solution comprises the following steps:
dissolving the aqueous solution of poly N-vinyl acetamide in water to obtain a solution A;
the aqueous solution of HF and Mn (NO)3)2And uniformly mixing the aqueous solution A with the solution A to obtain the polycrystalline silicon wafer texturing solution.
In a third aspect, the present invention provides a method for preparing a black silicon material, comprising:
and (3) placing a polycrystalline silicon wafer in the polycrystalline silicon wafer texturing solution for etching, and then cleaning to remove impurities to obtain the black silicon material.
Further, the etching is carried out in a constant-temperature water bath at 15-25 ℃.
Further, the etching time is 1-10 min.
Further, the method for cleaning and removing the impurities adopts an RCA standard cleaning method.
In a fourth aspect, the invention provides an application of the black silicon material obtained by the preparation method in a solar cell.
Further, the solar cell is a PERC cell.
Further, the black silicon material is used for accelerating the recovery of the polycrystalline silicon PERC battery LeTID.
The technical scheme of the invention has the following advantages:
1. the polycrystalline silicon slice texturing solution provided by the invention comprises HF and Mn (NO)3)2poly-N-vinylacetamide (PNVA) and water, HF and Mn (NO)3)2HNO is generated in the solution during mixing3，Mn2+Is HNO3By oxidation to Mn3+，HNO3And Mn3+To manyThe surface of the crystal silicon wafer plays a role in corrosion, meanwhile, the addition of poly N-vinyl acetamide (PNVA) further promotes the pore-forming effect of the texturing liquid, a nano microstructure can be formed on the surface of the polycrystalline silicon wafer, the texturing liquid for the polycrystalline silicon wafer is adopted, a damage layer does not need to be removed before texturing, the polycrystalline silicon wafer can be directly immersed into the texturing liquid for etching, rapid texturing is realized in a mild environment, the etched polycrystalline silicon wafer can be used for preparing a solar cell after being cleaned and impurities are removed, the use is convenient, and the texturing time is short.
2. According to the preparation method of the black silicon material, the polycrystalline silicon wafer is directly placed in the polycrystalline silicon wafer texturing liquid provided by the invention for etching, and is cleaned to remove impurities, so that the black silicon material with uniform appearance can be obtained.
3. The black silicon material prepared by the preparation method provided by the invention can be applied to solar cells, in particular to polycrystalline silicon PERC (passivated emitter and reactor cell) cells. When the black silicon material is used for a polycrystalline silicon PERC battery processing technology, compared with a polycrystalline silicon slice obtained by a conventional acid texturing technology, the black silicon material has the characteristic of accelerating the recovery of Light and heat attenuation (LeTID), can improve the power generation efficiency of the battery, provides a new solution for improving the ubiquitous LeTID phenomenon of the polycrystalline silicon PERC battery, and is beneficial to popularization and application of the polycrystalline silicon PERC battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a scanning electron micrograph of a black silicon material in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a black silicon material in example 2 of the present invention;
FIG. 3 is a scanning electron micrograph of a black silicon material in example 3 of the present invention;
FIG. 4 is a scanning electron micrograph of a black silicon material in example 4 of the present invention;
FIG. 5 is a scanning electron micrograph of a black silicon material in example 5 of the present invention;
FIG. 6 is a scanning electron micrograph of a black silicon material according to comparative example 1 of the present invention;
FIG. 7 is a graph of the reflectance of black silicon material in comparative example 1 and examples 1-5;
FIG. 8 shows SiN deposition on black silicon material in example 4 and comparative example 2 of the present inventionxA reflectance curve behind the passivation layer;
FIG. 9 shows the minority carrier lifetime trend of the black silicon texturing group and the conventional acid texturing group in the experimental example 4 of the present invention at 85% irradiation power.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
Reagent and instrument sources
An aqueous solution of HF, 500mL in specification, 40 wt% in concentration, purchased from the institute of chemical reagents, Beijing;
concentrated sulfuric acid with the specification of 500mL and the concentration of 98 wt% is purchased from the research institute of Beijing chemical reagents;
ammonia water with the specification of 500mL and the concentration of 25-28 wt% is purchased from the research institute of Beijing chemical reagents;
hydrogen peroxide, 500mL specification, 30 wt% concentration, purchased from the institute of chemical reagents, Beijing;
Mn(NO3)2500mL, 50 wt% strength aqueous solution from Michael;
an aqueous solution of PNVA, specification GE-191-107, concentration 10 wt%, viscosity 100-400mPa s, available from GE;
polycrystalline silicon wafer, boron doped, resistivity 1-3 Ω cm, available from suzhou synxin silicon materials science and technology development ltd;
a solar cell spectral response/QE/IPCE test system, model QEX7, available from PV Measurements inc;
the light attenuation furnace is customized for a laboratory and purchased from Jincheng sunshine SolarRay;
minority carrier lifetime instrument, model WCT-120, purchased from Sinton.
The RCA standard cleaning method is a wet chemical cleaning method commonly used in the field, and comprises the following specific steps:
(1) SPM of H2SO4And H2O2According to the following steps of 4: 1, 10-20min at 75-80 ℃, and effectively removing organic impurities;
(2) DHF, i.e. dilute HF solution, HF: H2The volume ratio of O is 1: 100-1: 250, 10-30s, and effectively removing a natural oxide layer and metal ions on the surface of the silicon wafer;
(3) SC-1, i.e. liquid No. one, from NH3·H2O、H2O2And H2O is as follows 5: 1: 5 volume ratio, 5min, 85 ℃, removing residual particles remained on the surface of the silicon wafer;
(4) SC-2, i.e. second liquid, from HCl, H2O2And H2O is as follows 1: 1: 6, removing metal impurity residues on the surface of the silicon wafer at 85 ℃ for 10-20 min;
(5) DHF for 10-30s, and removing an oxide layer on the surface of the silicon wafer;
after each step, the mixture is washed with deionized water for several times until no solution remains, and finally dried.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
A polycrystalline silicon texturing solution is prepared by the following steps:
(1) dissolving 1mL of PNVA aqueous solution in 8mL of water;
(2) taking 16mL of HF aqueous solution and Mn (NO)3)2Adding 64mL of the aqueous solution into the solution obtained in the step (1), and uniformly mixing to obtain a polycrystalline silicon texturing solution (wherein the molar concentration of HF is 4.24mol/L, and Mn (NO)3)2The molar concentration of (3.1 mol/L).
A black silicon material is prepared by the following steps:
(1) placing the prepared polycrystalline silicon texturing solution in a constant-temperature water bath kettle at 25 ℃;
(2) placing a polycrystalline silicon wafer in the polycrystalline silicon wafer texturing liquid for etching for 3 min;
(3) and cleaning the etched polycrystalline silicon wafer by adopting an RCA standard cleaning method to remove impurities, and drying to obtain the black silicon material.
FIG. 1 is a scanning electron microscope image of the black silicon material prepared in example 1, as shown in FIG. 1, the surface of the polysilicon forms a black silicon structure, and a thin porous layer exists.
Example 2
A polycrystalline silicon texturing solution is prepared by the following steps:
(1) dissolving 8mL of PNVA aqueous solution in 16mL of water;
(2) taking 16mL of HF aqueous solution and Mn (NO)3)2Adding 64mL of the aqueous solution into the solution obtained in the step (1), and uniformly mixing to obtain a polycrystalline silicon texturing solution (wherein the molar concentration of HF is 3.63mol/L, and Mn (NO)3)2The molar concentration of (2.6 mol/L).
A black silicon material is prepared by the following steps:
(1) placing the prepared polycrystalline silicon texturing solution in a constant-temperature water bath kettle at 15 ℃;
(2) placing a polycrystalline silicon wafer in the polycrystalline silicon wafer texturing liquid for etching for 3 min;
(3) and cleaning the etched polycrystalline silicon wafer by adopting an RCA standard cleaning method to remove impurities, and drying to obtain the black silicon material.
Fig. 2 is a scanning electron microscope image of the black silicon material prepared in example 2, as shown in fig. 2, a black silicon structure is formed on the surface of the polysilicon, and a porous layer with a certain thickness exists.
Example 3
A polycrystalline silicon texturing solution is prepared by the following steps:
(1) dissolving 4mL of PNVA aqueous solution in 8mL of water;
(2) taking 16mL of HF aqueous solution and Mn (NO)3)2Adding 64mL of the aqueous solution into the solution obtained in the step (1), and uniformly mixing to obtain a polycrystalline silicon texturing solution (wherein the molar concentration of HF is 4.24mol/L, and Mn (NO)3)2The molar concentration of (3.1 mol/L).
A black silicon material is prepared by the following steps:
(1) placing the prepared polycrystalline silicon texturing solution in a constant-temperature water bath kettle at 18 ℃;
(2) placing a polycrystalline silicon wafer in the polycrystalline silicon wafer texturing liquid for etching for 1 min;
(3) and cleaning the etched polycrystalline silicon wafer by adopting an RCA standard cleaning method to remove impurities, and drying to obtain the black silicon material.
FIG. 3 is a scanning electron micrograph of the black silicon material prepared in example 3, and as shown in FIG. 3, the surface of the polysilicon forms a black silicon structure, but the damaged layer is still observed.
Example 4
A polycrystalline silicon texturing solution is prepared by the following steps:
(1) dissolving 4mL of PNVA aqueous solution in 8mL of water;
(2) taking 16mL of HF aqueous solution and Mn (NO)3)2Adding 64mL of the aqueous solution into the solution obtained in the step (1), and uniformly mixing to obtain a polycrystalline silicon texturing solution (wherein the molar concentration of HF is 4.24mol/L, and Mn (NO)3)2The molar concentration of (3.1 mol/L).
A black silicon material is prepared by the following steps:
(1) placing the prepared polycrystalline silicon texturing solution in a constant-temperature water bath kettle at 18 ℃;
(2) placing a polycrystalline silicon wafer in the polycrystalline silicon wafer texturing liquid for etching for 5 min;
(3) and cleaning the etched polycrystalline silicon wafer by adopting an RCA standard cleaning method to remove impurities, and drying to obtain the black silicon material.
FIG. 4 is a scanning electron micrograph of the black silicon material prepared in example 4, and as shown in FIG. 4, a black silicon structure is formed on the surface of the polysilicon.
Example 5
A polycrystalline silicon texturing solution is prepared by the following steps:
(1) dissolving 4mL of PNVA aqueous solution in 8mL of water;
(2) taking 16mL of HF aqueous solution and Mn (NO)3)2Adding 64mL of the aqueous solution into the solution obtained in the step (1), and uniformly mixing to obtain a polycrystalline silicon texturing solution (wherein the molar concentration of HF is 4.24mol/L, and Mn (NO)3)2The molar concentration of (3.1 mol/L).
A black silicon material is prepared by the following steps:
(1) placing the prepared polycrystalline silicon texturing solution in a constant-temperature water bath kettle at 18 ℃;
(2) placing a polycrystalline silicon wafer in the polycrystalline silicon wafer texturing liquid for etching for 10 min;
(3) and cleaning the etched polycrystalline silicon wafer by adopting an RCA standard cleaning method to remove impurities, and drying to obtain the black silicon material.
Fig. 5 is a scanning electron microscope image of the black silicon material prepared in example 5, as shown in fig. 5, a black silicon structure is formed on the surface of the polysilicon, and the surface microstructure begins to disappear, so that a porous layer with a certain thickness is generated.
Comparative example 1
The preparation method of the black silicon material is different from that of the black silicon material in example 1 only in that the polycrystalline silicon texturing solution is prepared by the following method:
taking 16mL of HF aqueous solution and Mn (NO)3)264mL of the aqueous solution and 8mL of the aqueous solution are uniformly mixed to obtain a polycrystalline silicon texturing solution (wherein the molar concentration of HF is 4.29mol/L, and Mn (NO) is obtained3)2The molar concentration of (3.13 mol/L).
Fig. 6 is a scanning electron microscope image of the black silicon material in comparative example 1, and as shown in fig. 6, no significant black silicon structure is formed on the surface of the polysilicon, and a damaged layer is present.
Comparative example 2
A black silicon material is prepared by the following steps:
(1) using a catalyst containing 5.8mol/L HNO3And 1.18mol/L HF mixed solution to remove the surface damage layer of the polycrystalline silicon wafer;
(2) placing the polycrystalline silicon slice in a container containing 0.002mol/L AgNO3And 0.4mol/L HF mixed solution, depositing silver nano particles on the surface of the silicon wafer through local electrochemical reaction;
(3) putting the polycrystalline silicon wafer loaded with the silver nano-particles obtained in the step (2) into a reactor containing 0.77mol/L HF and 0.34mol/L H2O2The mixed etching solution is subjected to chemical corrosion for 10 min;
(4) soaking the polycrystalline silicon wafer obtained in the step (3) in concentrated nitric acid with the concentration of 65 wt% for 3min to remove silver nanoparticles;
(5) using a catalyst containing 9mol/L HNO3And 0.05mol/L HF mixed solution is used for carrying out correction etching treatment on the polycrystalline silicon chip obtained in the step (4);
(6) and (5) cleaning the polycrystalline silicon wafer obtained in the step (5) by adopting an RCA standard cleaning method to remove impurities, and drying to obtain the black silicon material.
Experimental example 1
The reflectance of the black silicon materials prepared in examples 1 to 5 and comparative example 1 was measured. The solar cell spectral response/QE/IPCE test system is used for detection, the wavelength range is 400 and 1100nm, and the obtained reflectivity curve is shown in FIG. 7.
As shown in fig. 7, the black silicon materials prepared in examples 1 to 5 all had significantly lower reflectance than comparative example 1, demonstrating that the addition of PNVA has a significant effect on reducing the reflectance of the black silicon material. Among them, example 4 is the most preferable example, and has the lowest reflectance under each wavelength measurement condition.
Experimental example 2
The reflectivity of the black silicon materials prepared in the embodiment 4 and the comparative example 2 after the SiNx passivation is detected, and the passivation process conditions are as follows: depositing double-sided silicon nitride by adopting a plasma chemical vapor deposition (PECVD) process, wherein the pressure is 0.2torr, the temperature is 400 ℃, the power is 110W, and the gas flow ratio NH is3/SiH4＝2010(sccm), deposition time 8.6min, thickness about 80 nm. The solar cell spectral response/QE/IPCE test system is used for detection, the wavelength range is 400 and 1100nm, and the obtained reflectivity curve is shown in FIG. 8.
As can be seen from fig. 8, the black silicon material prepared by the method of the present invention has a smaller difference in reflectivity than the black silicon material prepared by the conventional metal-assisted etching method (comparative example 2), i.e., the method of the present invention simplifies the process steps and avoids metal contamination under the condition of achieving a low reflectivity equivalent to that of the conventional black silicon material, and has the advantages of mild preparation conditions, simplified process, convenient and fast preparation, low cost, environmental friendliness, strong compatibility with a production line, and suitability for large-scale processing and production.
Experimental example 3
The black silicon material is prepared by the preparation method provided in the embodiment 4, and is processed by a phosphorus diffusion process and a double-sided passivation process in sequence to obtain the black silicon texture etching group minority carrier lifetime slice. The specific process parameters are as follows: in the phosphorus diffusion process, POCl is adopted at the temperature of 900 DEG C3Carrying out phosphorus diffusion; in the double-sided passivation process, firstly, an Atomic Layer Deposition (ALD) process is adopted to deposit double-sided alumina with the pressure of 0.15torr, the temperature of 200 ℃, the power of 80W and the thickness of about 15nm, and then a plasma chemical vapor deposition (PECVD) process is adopted to deposit double-sided silicon nitride with the pressure of 0.2torr, the temperature of 400 ℃, the power of 110W and the gas flow ratio NH3/SiH4Deposition time 8.6min at 20/10(sccm) was approximately 80nm thick. And (4) after passivation, performing an annealing process by using a muffle furnace, wherein the annealing temperature is 400 ℃, and the annealing time is 20 min.
For comparison, the same batch of diamond wire-cut polycrystalline silicon wafers as in example 4 was processed according to the conventional acid texturing method:
(1) using a catalyst containing 5.8mol/L HNO3Texturing a polycrystalline silicon wafer by using a mixed solution of 1.18mol/L HF, and controlling the reaction temperature to be below 10 ℃;
(2) cleaning with deionized water to remove an acid solution, then placing the solution in a 5% by weight KOH solution, and removing a metastable porous structure formed on the surface in the texturing process;
(3) after washing, immersing the silicon wafer into a mixed solution of 3.4mol/L HCl and 4.7mol/L HF for soaking and cleaning to remove metal impurities on the surface of the silicon wafer;
(4) soaking the silicon wafer for 10 to 30 seconds by using 0.5mol/L HF (hydrogen fluoride), removing an oxide layer on the surface of the silicon wafer, cleaning the silicon wafer by using deionized water and drying the silicon wafer.
And (3) treating the polycrystalline silicon wafer subjected to the texturing by using the conventional acid by adopting the same phosphorus diffusion process and double-sided passivation process to obtain the minority carrier lifetime slice subjected to the texturing by using the conventional acid.
The light attenuation furnace accelerates the LeTID test on the two groups of minority carrier lifetime slices: the belt speed is 4m/min, the irradiation intensity is 85% of the highest intensity of the equipment, and the irradiation temperature is 30-70 ℃.
Fig. 9 shows the minority carrier lifetime trend of the black silicon texturing group and the conventional acid texturing group at 85% irradiation power, as shown in fig. 9, the black silicon texturing group has a faster leid recovery stage than the conventional acid texturing group, and the analysis may be caused by the following reasons: the black silicon material provided by the invention has a larger surface area, so that the black silicon material has higher doping amount in a phosphorus gettering process, and can enhance the phosphorus gettering effect, thereby reducing the concentration of metal impurities in the black silicon material.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. The polycrystalline silicon wafer texturing solution is characterized by comprising an HF aqueous solution and Mn (NO)3)2An aqueous solution of poly-N-vinylacetamide and water;
in the polycrystalline silicon wafer texturing solution, the concentration of HF is 3.63-4.24mol/L, and Mn (NO) is3)2The concentration of the N-vinyl acetamide is 2.6-3.1mol/L, and the volume fraction of the aqueous solution of the poly N-vinyl acetamide is 1% -8%.
2. The method for preparing the polycrystalline silicon wafer texturing solution according to claim 1, comprising:
the aqueous solution of HF and Mn (NO)3)2The aqueous solution of (2) and the aqueous solution of poly (N-vinylacetamide) are dissolved in water so that the concentration of the HF is 3.63 to 4.24mol/L and the Mn (NO) is3)2The concentration of the N-vinyl acetamide is 2.6-3.1mol/L, and the volume fraction of the aqueous solution of the poly N-vinyl acetamide is 1% -8%.
3. A preparation method of a black silicon material is characterized by comprising the following steps:
and (2) placing the polycrystalline silicon wafer into the polycrystalline silicon wafer texturing solution of claim 1 or the polycrystalline silicon wafer texturing solution obtained by the preparation method of claim 2, etching, and then cleaning to remove impurities to obtain the black silicon material.
4. The method for preparing the black silicon material according to claim 3, wherein the etching is performed in a thermostatic waterbath at 15-25 ℃ for 1-10 min.
5. The method for preparing the black silicon material as claimed in claim 3 or 4, wherein the method for cleaning and removing impurities adopts RCA standard cleaning method.
6. Use of the black silicon material obtained by the preparation method according to any one of claims 3 to 5 in a solar cell.
7. Use according to claim 6, wherein the solar cell is a PERC cell.
8. Use according to claim 7, wherein the black silicon material is used to accelerate the recovery of PERC battery LeTID.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911360376.2A CN111040766B (en) | 2019-12-25 | 2019-12-25 | Polycrystalline silicon wafer texturing solution, preparation method of black silicon material and application of black silicon material in accelerating PERC battery LeTID recovery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911360376.2A CN111040766B (en) | 2019-12-25 | 2019-12-25 | Polycrystalline silicon wafer texturing solution, preparation method of black silicon material and application of black silicon material in accelerating PERC battery LeTID recovery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111040766A CN111040766A (en) | 2020-04-21 |
| CN111040766B true CN111040766B (en) | 2021-05-25 |
Family
ID=70239808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911360376.2A Active CN111040766B (en) | 2019-12-25 | 2019-12-25 | Polycrystalline silicon wafer texturing solution, preparation method of black silicon material and application of black silicon material in accelerating PERC battery LeTID recovery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111040766B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102514017B1 (en) * | 2020-09-28 | 2023-03-23 | 고려대학교 산학협력단 | Method for wet texturing of solar cell substrate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569511A (en) * | 2011-12-31 | 2012-07-11 | 常州天合光能有限公司 | Texturing method of crystalline silicon solar cell |
| CN102660776A (en) * | 2012-05-09 | 2012-09-12 | 南京航空航天大学 | Method for preparing black silicon through Mn ion catalysis and corrosion |
| CN104342702A (en) * | 2013-08-05 | 2015-02-11 | 南京科乃迪科环保科技有限公司 | Auxiliary chemical composition for monocrystalline silicon or polycrystalline silicon acidic wool making |
| CN110265296A (en) * | 2019-06-25 | 2019-09-20 | 中国科学院电工研究所 | A kind of method of silicon chip erosion, the method in silicon chip surface preparation antireflective flannelette and the method in silicon chip surface etching special pattern |
| JP2019186339A (en) * | 2018-04-06 | 2019-10-24 | 常州時創能源科技有限公司Ｃｈａｎｇｚｈｏｕ Ｓｈｉｃｈｕａｎｇ Ｅｎｅｒｇｙ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ Ｃｏｒｐｏｒａｔｉｏｎ | Process of texturing polycrystalline black silicon |
| CN110518075A (en) * | 2018-05-22 | 2019-11-29 | 中国科学院宁波材料技术与工程研究所 | A kind of black silicon passivating film, preparation method and application |
-
2019
- 2019-12-25 CN CN201911360376.2A patent/CN111040766B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569511A (en) * | 2011-12-31 | 2012-07-11 | 常州天合光能有限公司 | Texturing method of crystalline silicon solar cell |
| CN102660776A (en) * | 2012-05-09 | 2012-09-12 | 南京航空航天大学 | Method for preparing black silicon through Mn ion catalysis and corrosion |
| CN104342702A (en) * | 2013-08-05 | 2015-02-11 | 南京科乃迪科环保科技有限公司 | Auxiliary chemical composition for monocrystalline silicon or polycrystalline silicon acidic wool making |
| JP2019186339A (en) * | 2018-04-06 | 2019-10-24 | 常州時創能源科技有限公司Ｃｈａｎｇｚｈｏｕ Ｓｈｉｃｈｕａｎｇ Ｅｎｅｒｇｙ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ Ｃｏｒｐｏｒａｔｉｏｎ | Process of texturing polycrystalline black silicon |
| CN110518075A (en) * | 2018-05-22 | 2019-11-29 | 中国科学院宁波材料技术与工程研究所 | A kind of black silicon passivating film, preparation method and application |
| CN110265296A (en) * | 2019-06-25 | 2019-09-20 | 中国科学院电工研究所 | A kind of method of silicon chip erosion, the method in silicon chip surface preparation antireflective flannelette and the method in silicon chip surface etching special pattern |
Non-Patent Citations (1)
| Title |
|---|
| 电化学腐蚀多晶硅衬底减反射效果研究;李兆辰等;《太阳能》;20131231(第02期);第54-57页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111040766A (en) | 2020-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2182556B1 (en) | Process for manufacturing solar cell | |
| US9583652B2 (en) | Method for the wet-chemical etching back of a solar cell emitter | |
| KR101513911B1 (en) | Method for manufacturing wafer for solar cell, method for manufacturing solar cell, and method for manufacturing solar cell module | |
| US9076903B2 (en) | Forming high-efficiency silicon solar cells using density-graded anti-reflection surfaces | |
| CN110459642A (en) | Passivation contact battery and preparation method thereof | |
| CN103700733A (en) | Cleaning treatment method of N-type crystalline silicon substrate of solar cell | |
| EP2697820A1 (en) | Wet-chemical systems and methods for producing black silicon substrates | |
| CN104701392A (en) | Preparation method of solar battery with low-reflectivity black silicon | |
| Es et al. | An alternative metal-assisted etching route for texturing silicon wafers for solar cell applications | |
| CN104480532B (en) | A kind of making herbs into wool preprocess method of Buddha's warrior attendant wire cutting polysilicon chip and making herbs into wool pretreatment silicon chip and its application | |
| CN111040766B (en) | Polycrystalline silicon wafer texturing solution, preparation method of black silicon material and application of black silicon material in accelerating PERC battery LeTID recovery | |
| Jung et al. | Novel double acidic texturing process for saw-damage-free kerfless multicrystalline silicon wafers | |
| CN107316917A (en) | A kind of method for the monocrystalline silicon suede structure for preparing antiradar reflectivity | |
| Han et al. | Wet-texturing process for a thin crystalline silicon solar cell at low cost with high efficiency | |
| Huo et al. | Inverted pyramid structures fabricated on monocrystalline silicon surface with a NaOH solution | |
| JP2013225552A (en) | Method for manufacturing wafer for solar cell, method for manufacturing solar cell, and method for manufacturing solar cell module | |
| JP5724718B2 (en) | Method for producing solar cell wafer, method for producing solar cell, and method for producing solar cell module | |
| JP6677678B2 (en) | Manufacturing method of high efficiency solar cell | |
| CN111139076B (en) | Application of chemical corrosion liquid in texturing of surface of silicon wafer | |
| Cho et al. | Enhanced boron gettering effect of n-type solar grade Si wafers by in situ oxidation | |
| CN107749402A (en) | The fault of construction detection method of pulling of crystals silicon chip | |
| Yu et al. | Effects and methods of the BRL removal in solar cell | |
| Zhou et al. | Acid texturing of large area multi-crystalline silicon wafers for solar cell fabrication | |
| CN114628539A (en) | Texturing method for diamond wire-cut polycrystalline silicon wafer, textured silicon wafer and solar cell | |
| Yoo | Solar cell fabrication using edge-defined film-fed growth (EFG) silicon wafers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |