CN112838140B - Polycrystalline silicon solar cell, preparation method thereof and method for preparing textured structure of polycrystalline silicon solar cell - Google Patents
Polycrystalline silicon solar cell, preparation method thereof and method for preparing textured structure of polycrystalline silicon solar cell Download PDFInfo
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 112
- 239000010703 silicon Substances 0.000 claims abstract description 112
- 239000010410 layer Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910052709 silver Inorganic materials 0.000 claims abstract description 37
- 239000004332 silver Substances 0.000 claims abstract description 37
- 239000011241 protective layer Substances 0.000 claims abstract description 33
- -1 silver ions Chemical class 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000005530 etching Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910001868 water Inorganic materials 0.000 claims description 30
- 230000007797 corrosion Effects 0.000 claims description 22
- 238000005260 corrosion Methods 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 229920005591 polysilicon Polymers 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
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- 101710134784 Agnoprotein Proteins 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 8
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- 239000011148 porous material Substances 0.000 description 4
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- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021418 black silicon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—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
-
- 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
Abstract
The invention discloses a polycrystalline silicon solar cell, a preparation method and a method for preparing a textured structure of the polycrystalline silicon solar cell, wherein the method for preparing the textured structure of the polycrystalline silicon solar cell comprises the following steps: a, putting a silicon wafer into a solution containing metal silver ions, and forming a porous layer structure on the surface of the silicon wafer; b, putting the silicon wafer comprising the porous layer structure into HCL solution to form an AgCL protective layer; and c, putting the silicon wafer with the AgCL protective layer into a second etching solution to obtain the textured structure of the polycrystalline silicon solar cell. The method can reduce the proportion of the fuzzy yarns of the polycrystalline silicon solar cell and improve the light trapping effect and the cell conversion efficiency.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a method for preparing a textured structure of a polycrystalline silicon solar cell, a method for preparing the polycrystalline silicon solar cell and the polycrystalline silicon solar cell.
Background
The photovoltaic industry plays an important role in new energy development planning, and the polycrystalline silicon solar cell becomes the mainstream of the solar cell market at present. The quality of the texture surface on the surface of the silicon wafer has an important influence on the conversion efficiency of the solar cell, and the polycrystalline silicon surface texture making technology is increasingly paid attention by various countries in the world.
However, for a polycrystalline silicon wafer, because the raw materials have more impurities, and some defects exist during ingot casting, when a textured structure is prepared by adopting a black silicon texturing process, some composite centers which do not participate in photoelectric conversion exist, the proportion of the textured yarns of the polycrystalline silicon solar cell is increased, and the textured light trapping effect and the cell conversion efficiency are reduced.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, one object of the present invention is to provide a method for preparing a textured structure of a polycrystalline silicon solar cell, which can reduce the proportion of pile filaments of the polycrystalline silicon solar cell and improve the light trapping effect and the cell conversion efficiency.
The invention also aims to provide a method for preparing the polycrystalline silicon solar cell.
The invention also aims to provide a polycrystalline silicon solar cell.
In order to solve the above problems, a method for manufacturing a textured structure of a polycrystalline silicon solar cell according to an embodiment of the first aspect of the present invention includes: a, putting a silicon wafer into a solution containing metal silver ions, and forming a porous layer structure on the surface of the silicon wafer; b, putting the silicon wafer comprising the porous layer structure into HCL solution to form an AgCL protective layer; and c, putting the silicon wafer with the AgCL protective layer into a second etching solution to obtain the textured structure of the polycrystalline silicon solar cell.
According to the method for preparing the textured structure of the polycrystalline silicon solar cell, provided by the embodiment of the invention, the silicon wafer is subjected to hole digging treatment by adopting the solution containing metal silver ions, the silicon wafer with the porous layer structure is placed into the HCL solution, the HCL reacts with the silver ions, the AgCL protective layer is formed in the porous layer structure and is insoluble in the second corrosion solution, so that when the porous layer structure is modified by adopting the second corrosion solution to form the textured structure, the increase of the corrosion depth of the grain boundary and gully region of the porous layer structure, namely the increase of the defect or composite center can be effectively avoided by the protection of the AgCL protective layer, the proportion of pile fibers can be reduced, and the light trapping effect and the cell conversion efficiency can be improved.
In some embodiments, the step a comprises: and putting the silicon wafer into a hydrofluoric acid solution containing an oxidant and metal silver ions to form the porous layer structure on the surface of the silicon wafer.
In some embodiments, the step a comprises: soaking the silicon wafer in a solution containing metal silver ions to coat metal silver nanoparticles on the surface of the silicon wafer; and corroding the surface of the silicon wafer by adopting a first corrosion solution to form the porous layer structure on the surface of the silicon wafer, wherein the first corrosion solution is a mixed solution of hydrofluoric acid and an oxidant.
In some embodiments, AgNO is employed3、H2O2And HF forming the hydrofluoric acid solution containing the oxidant and the metal silver ions according to a preset mass percentage, wherein the AgNO3The value range of the mass percent is 2.0-7.5%; said H2O2The mass percentage of (A) is 1.0-5.0%; the mass percentage of the HF ranges from 15% to 25%.
In some embodiments, AgNO is employed3And HF forming the solution containing the metal silver ions according to a preset mass percentage, wherein the AgNO3The mass percent of the HF is 3-8%, and the mass percent of the HF is 0.1-0.3%; by means of H2O2And HF forming the first etching solution according to a preset mass percentage, wherein the H2O2The mass percent of the HF is 0.8-4.0%, and the mass percent of the HF is 10-20%.
In some embodiments, prior to the step a, the method further comprises: cleaning the silicon wafer and removing a damaged layer; or cleaning the silicon wafer, and removing the damaged layer of the cleaned silicon wafer.
In some embodiments, between steps a and b, and/or between steps b and c, the method further comprises: and (5) water washing.
In some embodiments, the concentration of the HCL solution ranges from 10% to 35%.
In some embodiments, the conditions of step b include: the reaction temperature is 65-75 deg.c and the reaction time is 30-160 s.
In some embodiments, the method for preparing the textured structure of the polycrystalline silicon solar cell further comprises the following steps: d, putting the silicon wafer with the textured structure of the polycrystalline silicon solar cell obtained in the step c into an ammonia solution for cleaning.
In some embodiments, the concentration of the aqueous ammonia solution ranges from 1.1% to 3%.
In some embodiments, the conditions of step d include: the cleaning time is 60-160 s, and the cleaning temperature is normal temperature.
In some embodiments, a water wash step is provided between step c and step d.
The method for preparing the polycrystalline silicon solar cell in the embodiment of the second aspect of the invention comprises the following steps: providing a polysilicon silicon wafer; preparing a textured structure on the polycrystalline silicon wafer by adopting the method for preparing the polycrystalline silicon solar textured structure in the embodiment; and preparing the photoelectric conversion structure on the polycrystalline silicon wafer with the textured structure.
According to the method for preparing the polycrystalline silicon solar cell, the textured structure is prepared by adopting the method for preparing the polycrystalline silicon solar textured structure, so that the cell conversion efficiency and the light trapping effect can be improved.
A polycrystalline silicon solar cell according to an embodiment of a third aspect of the present invention includes: a polysilicon silicon wafer; a textured structure and a photoelectric conversion structure are formed on the polycrystalline silicon wafer, wherein the textured structure is prepared by the method for preparing the textured structure of the polycrystalline silicon solar cell.
According to the polycrystalline silicon solar cell provided by the embodiment of the invention, the textured structure prepared by the method for preparing the polycrystalline silicon solar textured structure can reduce the proportion of the pile filaments and improve the photoelectric conversion efficiency and the light trapping effect.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a flow chart of a method for preparing a textured structure of a polycrystalline silicon solar cell according to one embodiment of the invention;
FIG. 2 is a detailed process flow diagram according to one embodiment of the present invention;
fig. 3 is a flow chart of a method of fabricating a polycrystalline silicon solar cell according to one embodiment of the present invention;
fig. 4 is a structural diagram of a polycrystalline silicon solar cell according to an embodiment of the present invention;
reference numerals:
a polycrystalline silicon solar cell 1;
a polysilicon silicon wafer 10; a suede structure 20; the photoelectric conversion structure 30.
Detailed Description
Embodiments of the present invention will be described in detail below, the embodiments described with reference to the drawings being illustrative, and the embodiments of the present invention will be described in detail below.
In order to solve the above problems, the method for manufacturing a textured structure of a polycrystalline silicon solar cell according to an embodiment of the first aspect of the present invention is described below with reference to the accompanying drawings, which can reduce a ratio of pile fibers, avoid an increase in corrosion depth of grain boundaries and a gully region of a porous layer structure, improve cell conversion efficiency, and have a good light trapping effect.
Fig. 1 is a flowchart of a method for manufacturing a textured structure of a polycrystalline silicon solar cell according to an embodiment of the invention. As shown in fig. 1, the method for preparing the textured structure of the polycrystalline silicon solar cell in the embodiment of the invention at least comprises steps a-c.
Step a, putting a silicon wafer into a solution containing metal silver ions, and forming a porous layer structure on the surface of the silicon wafer.
The silicon wafer is dug by adopting a metal ion wet etching process, namely, electrochemical corrosion is carried out on metal ions and contacted silicon atoms so as to directionally corrode the silicon wafer, so that a porous layer structure is formed on the surface of the silicon wafer, and in addition, as the solution contains metal silver ions, silver particles are attached to the formed porous layer structure.
In the embodiment, the silicon wafer is put into a hydrofluoric acid solution containing an oxidant and metal silver ions to form a porous layer structure on the surface of the silicon wafer. In particular, AgNO is used3、H2O2And HF, forming hydrofluoric acid solution containing oxidant and metal silver ions according to a preset mass percentage, putting the silicon wafer into the solution, accelerating directional corrosion, and forming a nano-scale microstructure on the surface of the silicon wafer, namely forming a nano-scale porous layer structure attached with silver particles, wherein the AgNO is3The mass percent of (A) is in the range of 2.0-7.5%, and H2O2The mass percent of (a) is in the range of 1.0-5.0%, and the mass percent of HF is in the range of 15-25%. For example, AgNO may be used3、H2O2And HF respectively in the mass percentages of 2.0%, 1.0% and 15% to form a mixed solution, or AgNO is adopted3、H2O2And HF respectively in the mass percentages of 3.0%, 3.0% and 20% to form a mixed solution, or AgNO is adopted3、H2O2And HF respectively forms a mixed solution according to the mass percentages of 7.5%, 5.0% and 25%, and the solution ratio can be adjusted within a value range according to circumstances to obtain a required porous layer structure.
Or soaking the silicon wafer in a solution containing metal silver ions to coat metal silver nanoparticles on the surface of the silicon wafer, and corroding the surface of the silicon wafer by using a first corrosion solution to form a porous layer structure on the surface of the silicon wafer, wherein the first corrosion solution is a mixed solution of hydrofluoric acid and an oxidant. In particular, AgNO is used3And HF forming a solution containing metallic silver ions at a predetermined mass percentage to form a silver-containing solution on siliconSilver particles are attached to the surface of the silicon wafer, and the silicon wafer attached with the silver particles is placed into a container adopting H2O2And HF forms a first corrosion solution according to a preset mass percentage, directional corrosion is accelerated, and a porous layer structure is formed, wherein AgNO is contained in the solution containing metal silver ions3The mass percent of the first etching solution is 3-8%, the mass percent of the HF is 0.1-0.3%, and the mass percent of the first etching solution is H2O2The mass percent of the hydrogen fluoride is 0.8-4.0%, and the mass percent of the HF is 10-20%. For example, AgNO may be used3HF forms a solution containing metal silver ions according to the mass percentage of 3 percent and 0.1 percent respectively, and H is adopted2O2And the HF forms a first etching solution according to the mass percentages of 0.8 percent and 10 percent respectively, or forms a mixed solution according to other mass percentages in a value range, and can be used for etching the silicon wafer to form a porous layer structure, specifically according to the situation.
The pore width of the porous layer structure may be 20nm to 50nm, and the pore depth may be 200nm to 500nm, and meanwhile, the shape of the porous layer structure may be adjusted according to the need or the corresponding concentration of the etching solution, so as to obtain the desired pore width and pore depth.
And b, putting the silicon wafer comprising the porous layer structure into HCL solution to form an AgCL protective layer.
Specifically, since the silicon wafer surface forming the porous layer structure contains silver particles and is placed in an HCL solution, the HCL will chemically react with the Ag particles in the porous layer structure, and an AgCL protective layer is formed in the porous layer structure, wherein since silver is discharged after hydrogen in the metal activity order table, the HCL solution needs to sufficiently react with the silver simple substance under the reaction condition of high concentration and high temperature to ensure that all the silver particles are reacted.
Specifically, the silicon wafer with the porous layer structure is placed into an HCL solution, wherein the concentration of the HCL solution is 10% -35%, preferably, the concentration range of the HCL solution is 30% -35%, the reaction temperature is 65 ℃ -75 ℃, and the reaction time is 30s-160s, and the chemical reaction can be carried out within the concentration range of the HCL solution and under the corresponding reaction conditions, so that all silver particles on the surface of the silicon wafer can be ensured to react, and an AgCL protective layer is formed.
For example, the silicon wafer forming the porous layer structure may be placed in a HCL solution with a solution concentration of 10% at a high temperature of 65 ℃ to continuously perform a chemical reaction for at least 30 seconds, or the silicon wafer forming the porous layer structure may be placed in a HCL solution with a solution concentration of 10% at a high temperature of 68 ℃ to continuously perform a chemical reaction for at least 30 seconds, or the silicon wafer forming the porous layer structure may be placed in a HCL solution with a solution concentration of 10% to continuously perform a chemical reaction for at least 30 seconds at a high temperature of 70 ℃ to form an AgCL protective layer, and the specific concentration of the HCL solution may be adjusted according to actual conditions such as the content of silver particles on the surface of the silicon wafer.
And c, putting the silicon wafer with the AgCL protective layer into a second etching solution to obtain the textured structure of the polycrystalline silicon solar cell.
In an embodiment, the second etching solution may be a mixed solution of a strong acid and an oxidizing agent, AgCl is insoluble in the second etching solution, and may include, for example and without limitation, a mixed solution of HF and an oxidizing agent, specifically, for example, HF and H2O2Or, HF and HNO3The mixed solution of (1).
Specifically, the silicon wafer with the AgCL protective layer is placed in a second corrosion solution, and in isotropic reaction of the solution, the surface of the porous layer structure is flattened and rounded, so that the porous layer structure is modified, and the textured structure of the polycrystalline silicon solar cell is formed.
Because the AgCL protective layer exists in the porous layer structure, the AgCL is not dissolved in the second corrosion solution, so the second corrosion solution can not continuously corrode the porous layer structure to the deep part, thereby effectively avoiding the increase of the corrosion depth of the grain boundary and gully regions, reducing the increase of defects or composite centers, namely reducing the proportion of the velvet filaments, wherein the defects or the composite centers can absorb light and convert the light into heat, reducing the photoelectric conversion rate, reducing the proportion of the velvet filaments by forming the AgCl protective layer in the porous layer structure, converting more received sunlight into electricity, and improving the light trapping effect of the velvet surface and the battery conversion efficiency.
According to the method for preparing the textured structure of the polycrystalline silicon solar cell, provided by the embodiment of the invention, the silicon wafer is subjected to hole digging treatment by adopting a solution containing silver ions, so that silver particles are attached to the surface of the porous layer structure, the silicon wafer with the porous layer structure is placed into the HCL solution, the HCL reacts with the silver ions, and the AgCL protective layer is formed in the porous layer structure and is insoluble in the second corrosion solution, so that when the porous layer structure is modified by adopting the second corrosion solution to form the textured structure, the increase of corrosion depths of a grain boundary and a gully region, namely the increase of defects or invalid composite centers, can be effectively avoided by the protection of the AgCL protective layer, the velvet ratio can be effectively reduced, and the conversion efficiency and the light trapping effect of the cell can be improved.
In some embodiments, because some contamination or scratches may exist on the surface of the original silicon wafer, before the texturing process is performed, that is, before the porous layer structure is formed on the silicon wafer, the silicon wafer is cleaned and the damaged layer is removed, or the silicon wafer is cleaned and the cleaned silicon wafer is subjected to the damaged layer removal process. For example, pure water or deionized water may be used to clean the original silicon wafer, and the cleaned silicon wafer may be subjected to a damage layer removal process, and then the silicon wafer with the damage layer removed may be subjected to a texturing process. The process of removing the damaged layer may include physical polishing, alkali etching, acid etching, etc., and the processing method is not limited.
In an embodiment, the method of an embodiment of the present invention, between steps a and b, and/or between steps b and c, further comprises a water washing step. Specifically, before the silicon wafer with the porous layer structure is placed in the HCL solution, the silicon wafer with the porous layer structure is placed in pure water for a first rinsing to remove the solution residue on the surface. And after the AgCL protective layer is formed in the porous layer structure, putting the silicon wafer with the AgCL protective layer formed in the porous layer structure into pure water for secondary rinsing to remove HCL solution residues, wherein the AgCL protective layer in the porous layer structure can be reserved because the AgCL in the porous layer structure is not dissolved in water.
Further, Ag (NH) is generated because AgCL can be dissolved in ammonia water3)2And (d) placing the silicon wafer with the textured structure of the polycrystalline silicon solar cell into an ammonia water solution for cleaning so as to remove the AgCL protective layer, wherein the method for preparing the textured structure of the polycrystalline silicon solar cell further comprises a step d, as shown in figure 1. Specifically, the silicon wafer is placed into an ammonia water solution to be cleaned for a certain time at normal temperature of 25 +/-5 ℃ to remove the AgCL protective layer in the porous layer structure, wherein the cleaning time is 60s-160s, the concentration of the ammonia water solution is 1.1% -3.0%, namely the volume ratio of the ammonia water solution with the mass fraction of 28% to water is 1: 15-1: 30, preferably, the concentration of the ammonia solution is in the range of 1.2% -1.8%. For example, the silicon wafer may be washed by putting the silicon wafer into ammonia water with a solution concentration of 1.1%, or the silicon wafer may be washed by putting the silicon wafer into ammonia water with a solution concentration of 1.25%, or the silicon wafer may be washed by putting the silicon wafer into ammonia water with a solution concentration of 3.0%, and the washing time is sufficient to ensure complete removal of the AgCL protective layer in the porous layer structure.
Further, after the textured structure is formed, the silicon wafer with the textured structure is placed into pure water to be rinsed for the third time to remove the second corrosion solution residues, the silicon wafer after being rinsed for the third time is placed into an ammonia water solution, and AgCL is dissolved in the ammonia water, so that an AgCL protective layer in the porous layer structure can be removed, and then the silicon wafer with the AgCL removed can normally enter subsequent processes such as diffusion and the like after being subjected to HF solution, pure water and drying to prepare the complete solar cell.
The following specifically describes a flow of the method for preparing the textured structure of the polycrystalline silicon solar cell according to the embodiment of the invention with reference to fig. 2, as shown in fig. 2, the detailed flow is as follows, wherein DI is pure water.
S7: and removing the damaged layer from the polycrystalline silicon wafer.
S8: rinsing is performed using pure water.
S9: and (3) carrying out hole digging treatment on the silicon wafer by using a wet black silicon process MCCE.
S10: rinsing is performed using pure water.
S11: put into HCL solution to create a protective layer of AgCL.
S12: rinsing is performed using pure water.
S13: put into HNO3And in the solution of HF system, suede modification is carried out to flatten and round the surface of the porous layer structure.
S14: rinsing is performed using pure water.
S15: in aqueous ammonia solution (RCA), i.e. NH3·H2O and H2O2Solution of system to remove AgCL.
S16: rinsing is performed using pure water.
S17: putting the silicon wafer into an HF solution to make the surface of the silicon wafer hydrophobic.
S18: rinsing is performed using pure water.
S19: and (5) drying.
For example, a polycrystalline silicon wafer is subjected to a damage layer removal, rinsed with pure water, and subjected to AgNO3、H2O2And HF respectively according to the mixed solution formed by the mass percentages of 2.0%, 1.0% and 15%, carrying out hole digging treatment on the silicon wafer to form a porous layer structure with the hole width of 20nm and the hole depth of 200nm, putting pure water for rinsing, putting the silicon wafer with the porous layer structure into HCL solution with the solution concentration of 10%, carrying out chemical reaction at the high temperature of 65 ℃, the reaction time is 30-160 s, ensuring that all silver particles react, forming an AgCL protective layer, putting the silicon wafer into the pure water for rinsing, putting the silicon wafer with the AgCL protective layer into second corrosive solution, modifying the porous layer structure to obtain a polycrystalline silicon solar cell textured structure, putting the silicon wafer into the pure water for rinsing, putting the silicon wafer with the polycrystalline silicon cell textured structure into ammonia solution with the solution concentration of 1.1% to remove the AgCL protective layer, further, the silicon wafer with AgCL removed can be usedAfter being dried by HF solution and pure water, the solar cell can normally enter the subsequent processes of diffusion and the like so as to prepare the complete solar cell.
For another example, a damaged layer is removed from a polycrystalline silicon wafer, the wafer is rinsed with pure water, and AgNO is used3、H2O2And HF respectively according to mixed solution formed by 6.0%, 4.0% and 20% by mass percentage, carrying out hole digging treatment on the silicon wafer to form a porous layer structure with the hole width of 30nm and the hole depth of 300nm, putting pure water for rinsing, putting the silicon wafer with the porous layer structure into HCL solution with the solution concentration of 33%, carrying out chemical reaction at the high temperature of 73 ℃, the reaction time is 30-160 s, ensuring that all silver particles react, forming an AgCL protective layer, putting the silicon wafer into pure water for rinsing, putting the silicon wafer with the AgCL protective layer into second corrosive solution, modifying the porous layer structure to obtain a polycrystalline silicon solar cell textured structure, putting the silicon wafer into pure water for rinsing, putting the silicon wafer with the polycrystalline silicon cell textured structure into ammonia solution with the solution concentration of 1.25% to remove the AgCL protective layer, and then the silicon wafer without the AgCL can normally enter subsequent processes such as diffusion and the like after being subjected to HF solution, pure water and drying so as to prepare a complete solar cell.
Through the embodiment, the flow of the method for preparing the textured structure of the polycrystalline silicon solar cell shown in fig. 2, the solution concentration ratio preset according to the actual situation and the reaction conditions are adopted to prepare the solar cell, the light trapping effect is excellent, the proportion of the textured yarns is small, and the conversion efficiency of the cell can be improved by at least 0.1%.
In summary, according to the method for preparing the textured structure of the polycrystalline silicon solar cell in the embodiment of the invention, the silver ion wet etching process is adopted to dig holes on the silicon wafer, the silicon wafer with the porous layer structure is placed into the HCL solution, the HCL reacts with the silver ions, an AgCL protection layer is formed in the porous layer structure, and, since the AgCL protection layer is insoluble in the second etching solution, the porous layer structure can be modified by a second corrosive solution, so that the surface of the porous layer structure is flattened, the porous layer structure is rounded, a suede structure is formed, due to the AgCL protective layer, the second corrosive solution can be effectively prevented from continuously corroding the porous layer structure deeply, the corrosion depth of the grain boundary and gully region is prevented from increasing, the proportion of the fluff is reduced, the sunlight received by the suede structure can be subjected to more photoelectric conversion, and the conversion efficiency and the light trapping effect of the battery are improved.
In a second aspect, the embodiment of the present invention provides a method for manufacturing a polycrystalline silicon solar cell, and as shown in fig. 3, the method for manufacturing a polycrystalline silicon solar cell of the embodiment of the present invention includes steps S4-S6.
And step S4, providing a polysilicon silicon wafer.
Step S5, a method for preparing a polysilicon solar textured structure provided in the first aspect of the present invention is used to prepare a textured structure on a polysilicon wafer, and the specific process may refer to the description of the foregoing embodiments.
Step S6: and preparing the photoelectric conversion structure on the polycrystalline silicon wafer with the textured structure.
In some embodiments, the solar cell is fabricated by performing the steps of texturing, diffusion or injection, etching, plating, and printing.
Specifically, texturing may be performed by the textured structure preparation method of the above embodiment, and a photoelectric conversion structure such as a PN junction may be prepared using a diffusion process. Taking thermal diffusion as an example, a polysilicon silicon wafer with a textured structure is placed into a diffusion furnace by taking a quartz boat as a carrier, and nitrogen and doping elements are introduced into the diffusion furnace at a certain temperature, so that PN junctions are diffused and deposited on the surface of the silicon wafer. When sunlight irradiates on the PN junction, a hole-electron pair is generated, under the influence of an electric field built in the PN junction, a photogenerated hole flows to the P area, and a photogenerated electron flows to the N area, so that photogenerated electromotive force appears on two sides of the PN junction, and photoelectric conversion is realized.
According to the method for preparing the polycrystalline silicon solar cell, the textured structure is prepared by adopting the method for preparing the polycrystalline silicon solar textured structure, so that the cell conversion efficiency and the light trapping effect can be improved.
A polycrystalline silicon solar cell 1 according to an embodiment of the present invention includes a polycrystalline silicon wafer 10, and a textured structure 20 and a photoelectric conversion structure 30 formed on the polycrystalline silicon wafer 10, as shown in fig. 4, where the textured structure 20 is prepared by the method for preparing a textured structure of a polycrystalline silicon solar cell provided in the above embodiment.
Specifically, when the surface of the polycrystalline silicon solar cell 1 is illuminated, the textured structure 20 absorbs sunlight, and the photoelectric conversion structure 30 converts the absorbed sunlight into electric energy, so as to realize the photoelectric conversion function of the polycrystalline silicon solar cell 1.
According to the polycrystalline silicon solar cell 1 provided by the embodiment of the invention, the textured structure 20 prepared by the method for preparing the polycrystalline silicon solar textured structure provided by the embodiment can reduce the proportion of the pile yarns and improve the photoelectric conversion efficiency and the light trapping effect.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (14)
1. A method for preparing a textured structure of a polycrystalline silicon solar cell is characterized by comprising the following steps:
a, putting a silicon wafer into a solution containing metal silver ions, and forming a porous layer structure on the surface of the silicon wafer;
b, putting the silicon wafer comprising the porous layer structure into an HCl solution to form an AgCL protective layer, wherein the concentration range of the HCl solution is 10% -35%, and the reaction temperature range is 65-75 ℃;
and c, putting the silicon wafer with the AgCL protective layer into a second etching solution to obtain the textured structure of the polycrystalline silicon solar cell.
2. The method for preparing the textured structure of the polycrystalline silicon solar cell according to claim 1, wherein the step a comprises the following steps: and putting the silicon wafer into a hydrofluoric acid solution containing an oxidant and metal silver ions to form the porous layer structure on the surface of the silicon wafer.
3. The method for preparing the textured structure of the polycrystalline silicon solar cell according to claim 1, wherein the method comprises the following steps: the step a comprises the following steps:
soaking the silicon wafer in a solution containing metal silver ions to coat metal silver nanoparticles on the surface of the silicon wafer;
and corroding the surface of the silicon wafer by adopting a first corrosion solution to form the porous layer structure on the surface of the silicon wafer, wherein the first corrosion solution is a mixed solution of hydrofluoric acid and an oxidant.
4. The method for preparing the textured structure of the polycrystalline silicon solar cell according to claim 2, wherein the method comprises the following steps: by AgNO3、H2O2And HF forming the hydrofluoric acid solution containing the oxidant and the metallic silver ions according to a preset mass percentage, wherein,
the AgNO3The value range of the mass percent is 2.0-7.5%;
said H2O2The mass percentage of (A) is 1.0-5.0%;
the mass percentage of the HF ranges from 15% to 25%.
5. The method for preparing the textured structure of the polycrystalline silicon solar cell according to claim 3,
by AgNO3And HF forming the solution containing the metal silver ions according to a preset mass percentage, wherein the AgNO3The mass percent of the HF is 3-8%, and the mass percent of the HF is 0.1-0.3%;
by the use of H2O2And HF forming the first etching solution according to a preset mass percentage, wherein the H2O2The mass percent of the HF is 0.8-4.0%, and the mass percent of the HF is 10-20%.
6. The method for preparing the textured structure of the polycrystalline silicon solar cell in claim 1, wherein before the step a, the method further comprises the following steps:
cleaning the silicon wafer and removing a damaged layer;
or cleaning the silicon wafer, and removing the damaged layer of the cleaned silicon wafer.
7. The method for preparing the textured structure of the polycrystalline silicon solar cell according to claim 1, wherein the method comprises the following steps: between steps a and b, and/or between steps b and c, the method further comprises: and (5) water washing.
8. The method for preparing the textured structure of the polycrystalline silicon solar cell according to claim 1, wherein the method comprises the following steps: the conditions of the step b comprise: the reaction time ranges from 30s to 160 s.
9. The method for preparing the textured structure of the polycrystalline silicon solar cell according to claim 1, wherein the method comprises the following steps: the method further comprises the following steps:
d, putting the silicon wafer with the textured structure of the polycrystalline silicon solar cell obtained in the step c into an ammonia solution for cleaning.
10. The method for preparing the textured structure of the polycrystalline silicon solar cell according to claim 9, wherein the method comprises the following steps: the concentration range of the ammonia water solution is 1.1% -3%.
11. The method for preparing the textured structure of the polycrystalline silicon solar cell according to claim 10, wherein the method comprises the following steps: the conditions of the step d comprise: the cleaning time is 60-160 s, and the cleaning temperature is normal temperature.
12. The method for preparing the textured structure of the polycrystalline silicon solar cell according to claim 9, wherein the method comprises the following steps: a water washing step is arranged between the step c and the step d.
13. A method of making a polycrystalline silicon solar cell, comprising:
providing a polysilicon silicon wafer;
preparing a textured structure on the polycrystalline silicon wafer by adopting the method for preparing the textured structure of the polycrystalline silicon solar cell according to any one of claims 1 to 12; and
and preparing the photoelectric conversion structure on the polycrystalline silicon wafer with the textured structure.
14. A polycrystalline silicon solar cell, comprising:
a polysilicon silicon wafer;
a textured structure and a photoelectric conversion structure are formed on the polycrystalline silicon wafer, wherein the textured structure is prepared by the method for preparing the textured structure of the polycrystalline silicon solar cell according to any one of claims 1 to 12.
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