CN114597270B - Heterojunction solar cell and preparation method and application thereof - Google Patents
Heterojunction solar cell and preparation method and application thereof Download PDFInfo
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- 239000000758 substrate Substances 0.000 claims abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 46
- 239000010703 silicon Substances 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 238000000151 deposition Methods 0.000 claims abstract description 37
- 238000004070 electrodeposition Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910000597 tin-copper alloy Inorganic materials 0.000 claims abstract description 31
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
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- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
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- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 claims description 11
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims description 11
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- 238000001035 drying Methods 0.000 claims description 10
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- 238000011065 in-situ storage Methods 0.000 abstract description 5
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- 229940051841 polyoxyethylene ether Drugs 0.000 description 11
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
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- 238000007792 addition Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 235000011152 sodium sulphate Nutrition 0.000 description 2
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- 238000009713 electroplating Methods 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
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- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
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- 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
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
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Abstract
The invention provides a heterojunction solar cell and a preparation method and application thereof, wherein the preparation method comprises the following steps: polymerizing a combination of 3, 4-ethylenedioxythiophene and styrene sulfonic acid monomers serving as monomers on a silicon substrate provided with a transparent conductive layer to obtain a polymer conductive film; and electrochemically depositing a tin-copper alloy layer on the polymer conductive film to form a metal grid line, thereby obtaining the heterojunction solar cell. The invention prepares the tin-copper alloy grid line by the electrochemical deposition process, obviously reduces the manufacturing cost, enables the metal grid line to have better conductivity and stability, and does not need to be provided with an outer protective layer. The preparation method adopts an in-situ polymerization mode to form the PEDOT, namely the PSS high-molecular conductive film which is used as a bonding layer of the transparent conductive layer and the metal grid line, can effectively improve the conductivity and the platability, prevent the damage to TCO in laser etching, prevent copper ions from migrating to a cell and effectively improve the comprehensive performance of the heterojunction solar cell.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a heterojunction solar cell and a preparation method and application thereof.
Background
Due to the non-renewable property of the traditional petrochemical energy and the atmospheric problems caused by the use process of the traditional petrochemical energy, green and renewable energy is paid more and more attention. Green, renewable energy sources including solar, wind, water, etc., particularly solar energy, are considered to be inexhaustible, green energy sources. The solar energy is collected mainly through the solar cell, and the solar cell converts solar light energy into electric energy to meet daily life of people. The solar cell has undergone rapid development since the emergence of the crystalline silicon cell, the current commercial cell can reach more than 24% of conversion efficiency, and the efficiency improvement technology in the future is continuously researched and developed.
The heterojunction solar cell generally includes a monocrystalline silicon substrate, intrinsic amorphous silicon layers respectively disposed on both sides of the monocrystalline silicon substrate, a p-type amorphous silicon layer and an n-type amorphous silicon layer disposed on the intrinsic amorphous silicon layer; transparent conducting layers are respectively arranged on the p-type amorphous silicon layer and the n-type amorphous silicon layer, and grid line electrodes are arranged on the transparent conducting layers. In the manufacturing process of the solar cell, the grid line metallization process is one of very important preparation steps, and the size of the grid line influences the light absorption area of the solar cell panel, so that the grid line is also the key direction for improving the cell efficiency.
CN110649128A discloses a method for preparing a high-efficiency heterojunction cell, which comprises the steps of performing laser precutting on the front surface of a silicon wafer for preparing the cell to form a cutting groove, and then sequentially performing the following steps: texturing, forming specific amorphous silicon on the front surface and the back surface, plating a Transparent Conducting Oxide (TCO) film, printing a grid line electrode and curing to obtain the heterojunction battery piece. CN112599645A discloses a preparation process of a silicon heterojunction solar cell, which comprises: cleaning a silicon wafer, depositing amorphous silicon, depositing a TCO film, annealing before screen printing, and annealing after screen printing; the preparation process adds an annealing process before screen printing, which is beneficial to improving the filling factor of the solar cell and improving the reliability of the assembly.
At present, the technology of screen printing silver paste is mainly adopted in industry to prepare the grid line electrode, then the organic matter in the silver paste is volatilized by a rapid sintering method, and the silver is solidified to form the metal electrode. The process method is simple and mature, and is applied in a large scale; but also the following non-negligible drawbacks exist: (1) in order to sinter and form, a glass phase is usually required to be added into silver paste, so that the sintered silver grid line electrode is of a silver porous continuous structure, and the volume resistance of the sintered silver grid line electrode is large; (2) a non-conductive reaction layer is formed between the silver and the silicon at the bottom layer in the sintering process, so that the contact resistance is increased; (3) the screen printing has certain requirements on the line width and the line height, is limited by the size of a screen template, and cannot further reduce the line width of grid lines to improve the effective area of a battery; (4) silver belongs to noble metals, and particularly in the aspect of low-temperature silver paste used in a heterojunction battery, the preparation of a silver nano material is limited by imported products, so that the price of the low-temperature silver paste is very high, the cost of the battery is increased, and the large-scale application of the battery is limited.
Therefore, it is an urgent problem in the art to develop a manufacturing process capable of reducing the manufacturing cost of a battery and improving the performance of the battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a heterojunction solar cell and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for fabricating a heterojunction solar cell, the method comprising: polymerizing a combination of 3, 4-ethylenedioxythiophene and styrene sulfonic acid monomers serving as monomers on a silicon substrate provided with a transparent conductive layer to obtain a polymer conductive film; and electrochemically depositing a tin-copper alloy layer on the polymer conductive film to form a metal grid line, thereby obtaining the heterojunction solar cell.
According to the preparation method of the Heterojunction (HJT) solar cell, the existing low-temperature silver paste process is replaced by the novel electrochemical deposition process, and the tin-copper alloy layer is used as the metal grid line, so that the manufacturing cost of the cell is remarkably reduced, and the obtained metal grid line has better conductivity; and the metal grid line has good stability, and an outer protective layer (such as a silver protective layer) is not required to be arranged. As a process matched with electrochemical deposition, the preparation method provided by the invention adopts an in-situ polymerization mode to form a high polymer conductive film on a transparent conductive layer (TCO), wherein the high polymer conductive film is PEDOT (PSS) formed by copolymerizing 3, 4-Ethylenedioxythiophene (EDOT) and styrene sulfonic acid monomers (SS), and the PSS conductive layer is used as a bonding layer of the transparent conductive layer and a metal grid line, so that the conductivity of the transparent conductive layer can be effectively improved, and the platability is increased; meanwhile, the polymer conductive film can prevent damage to TCO (transparent conductive oxide) during preparation of grid line patterns (laser etching), and prevent copper ions from migrating to the cell, so that the obtained heterojunction solar cell has higher open-circuit voltage and cell efficiency, and the comprehensive performance of the heterojunction solar cell is improved.
In the present invention, the silicon substrate provided with a transparent conductive layer (TCO) can be purchased commercially or prepared in a manner known in the art; for the sake of brevity, the present invention is not described in detail.
Preferably, the material of the transparent conductive layer is a transparent conductive material known In the art, and exemplarily includes but is not limited to ITO (indium tin oxide), In 2 O 3 、In 2 O 3 :W（IWO）、ZnO、SnO 2 Or any one or a combination of at least two of PEDOT and PSS, and further preferably ITO. The transparent conductive layer can be disposed on the silicon substrate by coating, sputtering, thermal evaporation, electron beam evaporation, reactive plasma deposition, printing, chemical vapor deposition, printing, czochralski methods, and the like, as known in the art.
The molar ratio of the 3, 4-ethylenedioxythiophene to the styrene sulfonic acid monomer is preferably 1 (0.5-4), and may be, for example, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5, or 1:3.8, and more preferably 1 (1.5-3).
Preferably, the styrene sulfonic acid monomer is styrene sulfonic acid and/or styrene sulfonate, and further preferably styrene sulfonic acid and/or sodium styrene sulfonate.
Preferably, the thickness of the polymer conductive film is 0.05-0.2 μm, for example, 0.06 μm, 0.08 μm, 0.1 μm, 0.12 μm, 0.15 μm, 0.18 μm or 0.2 μm, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
As a preferred technical scheme of the invention, the thickness of the polymer conductive film (PEDOT: PSS conductive film) is 0.05-0.2 μm, and the polymer conductive film is used as a bonding layer of TCO and a metal grid line, so that the conductivity of the TCO can be improved, the platability is increased, the damage to the TCO when a grid line pattern is formed by laser etching can be prevented, the migration of copper ions to a cell is inhibited, and the open-circuit voltage and the efficiency of the heterojunction solar cell are improved. If the thickness of the polymer conductive film is too low, the effect of improving the conductivity and the platability is not obvious; if the thickness of the polymer conductive film is too high, the impedance of the cell in the transmission process during working can be increased, and the transparency is reduced, so that the comprehensive performance of the heterojunction solar cell is influenced.
Preferably, the method of polymerization is an emulsion polymerization method.
Preferably, the method of polymerization comprises: soaking the silicon substrate provided with the transparent conducting layer in the monomer mixed solution, and then carrying out polymerization reaction to obtain the polymer conducting film; the monomer mixed solution comprises a monomer, an emulsifier, an initiator and water.
Preferably, the concentration of the monomer in the monomer mixture is 0.1-0.5 mol/L, for example, 0.12 mol/L, 0.15 mol/L, 0.18 mol/L, 0.2 mol/L, 0.22 mol/L, 0.25 mol/L, 0.28 mol/L, 0.3 mol/L, 0.32 mol/L, 0.35 mol/L, 0.38 mol/L, 0.4 mol/L, 0.42 mol/L, 0.45 mol/L or 0.48 mol/L, and the specific values therebetween are not exhaustive, and for the sake of brevity.
Preferably, the concentration of the 3, 4-ethylenedioxythiophene in the monomer mixture is 0.05-0.2 mol/L, for example, 0.06 mol/L, 0.08 mol/L, 0.1 mol/L, 0.11 mol/L, 0.13 mol/L, 0.15 mol/L, 0.17 mol/L or 0.19 mol/L, and the specific values therebetween are limited by space and for the sake of brevity, and the invention does not exhaust the specific values included in the range.
Preferably, the concentration of the styrene sulfonic acid monomer in the monomer mixture is 0.1-0.3 mol/L, for example, 0.11 mol/L, 0.13 mol/L, 0.15 mol/L, 0.17 mol/L, 0.19 mol/L, 0.2 mol/L, 0.21 mol/L, 0.23 mol/L, 0.25 mol/L, 0.27 mol/L or 0.29 mol/L, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the emulsifier is an anionic surfactant.
Preferably, the concentration of the emulsifier in the monomer mixture is 1.0-4.0 g/L, such as 1.2 g/L, 1.5 g/L, 1.8 g/L, 2.0 g/L, 2.2 g/L, 2.5 g/L, 2.8 g/L, 3.0 g/L, 3.2 g/L, 3.5 g/L, 3.8 g/L, 4.0 g/L, 4.2 g/L, 4.5 g/L or 4.8 g/L, and the specific values therebetween are not exhaustive and for the sake of brevity.
Preferably, the emulsifier comprises a combination of sodium diphenylethylene phenol polyoxyethylene ether sulfonate and sodium isooctyl alcohol sulfate.
Preferably, the concentration of the sodium diphenylethylene phenol polyoxyethylene ether sulfonate in the monomer mixture is 0.5-3.0 g/L, for example, 0.6 g/L, 0.8 g/L, 1.0 g/L, 1.2 g/L, 1.5 g/L, 1.8 g/L, 2.0 g/L, 2.2 g/L, 2.5 g/L or 2.8 g/L, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the concentration of sodium isooctanoate sulfate in the monomer mixture is 0.1-1.0 g/L, for example, 0.2 g/L, 0.3 g/L, 0.4 g/L, 0.5 g/L, 0.6 g/L, 0.7 g/L, 0.8 g/L or 0.9 g/L, and the specific values therebetween are not exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the initiator is a persulfate.
Preferably, the initiator comprises any one of ammonium persulfate, potassium persulfate or sodium persulfate, or a combination of at least two thereof.
Preferably, the concentration of the initiator in the monomer mixture is 0.001-0.1 g/L, such as 0.003 g/L, 0.005 g/L, 0.008 g/L, 0.01 g/L, 0.02 g/L, 0.03 g/L, 0.04 g/L, 0.05 g/L, 0.06 g/L, 0.07 g/L, 0.08 g/L or 0.09 g/L, and the specific values therebetween are not exhaustive, and for brevity, the invention is not intended to be exhaustive.
Preferably, the soaking time is 5-20 min, for example, 6 min, 8 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min or 19 min, and the specific values therebetween are limited by space and for the sake of brevity, the invention is not exhaustive.
Preferably, the soaking temperature is 10-40 ℃, for example, 12 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃ or 38 ℃, and the specific values therebetween are limited by space and conciseness, and the invention is not exhaustive list of the specific values included in the range, and more preferably 15-30 ℃, and more preferably room temperature.
Preferably, the polymerization temperature is 70 to 120 ℃, for example, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃ or 115 ℃, and the specific values therebetween are limited for brevity and conciseness, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the polymerization time is 10 to 120 s, for example, 20 s, 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s or 110 s, and the specific values therebetween are not exhaustive, and for brevity and conciseness, the invention does not provide for the specific values included in the range, and more preferably 30 to 90 s.
Preferably, a drying step is further included between the soaking and the polymerization reaction.
Preferably, the method of polymerization comprises: soaking the silicon substrate provided with the transparent conducting layer in the monomer mixed solution, and then carrying out heat treatment at 70-120 ℃ for 10-120 s to carry out reaction to obtain the polymer conducting film; the monomer mixed solution comprises a monomer, an emulsifier, an initiator and water; the concentration of the monomer in the monomer mixed solution is 0.1-0.5 mol/L, and the concentration of the emulsifier is 1.0-4.0 g/L.
As a preferred technical scheme of the invention, the monomer mixed solution comprises a monomer (a combination of 3, 4-ethylenedioxythiophene and styrene sulfonic acid monomers), an emulsifier, an initiator and water, and the monomer mixed solution can be expanded and uniformly distributed on the surface of the silicon substrate provided with the transparent conductive layer in the soaking process by controlling the concentration and the addition amount of each component in the monomer mixed solution and utilizing the surface tension; and then carrying out heat treatment to obtain the transparent polymer conductive film with controllable thickness (0.05-0.2 μm).
Preferably, the silicon substrate provided with the transparent conductive layer is a surface-treated silicon substrate provided with a transparent conductive layer.
Preferably, the surface treatment agent is an acid solution, more preferably a sulfuric acid solution.
Preferably, the concentration of the acid solution (sulfuric acid solution) is 1-8%, for example, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, or 7.5%, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the surface treatment time is 1-30 min, for example, 2 min, 5 min, 8 min, 10 min, 12 min, 15 min, 18 min, 20 min, 22 min, 25 min or 28 min, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
As a preferred technical scheme of the present invention, the silicon substrate provided with the transparent conductive layer is subjected to surface treatment with an acid solution, so that the transparent conductive layer is activated and has positive charges, which is helpful for surface adsorption and distribution of monomers when the silicon substrate is soaked in a monomer mixed solution, thereby forming a polymer conductive film with controllable thickness.
Preferably, the deposition solution for electrochemical deposition comprises copper pyrophosphate, tin pyrophosphate, potassium dihydrogen phosphate and water.
Preferably, the pH of the deposition solution is 8.5-9.5, and may be, for example, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, or 9.4, and the specific values therebetween, are not intended to be exhaustive, and for the sake of brevity and clarity, and are not intended to be exhaustive.
Preferably, the concentration of copper pyrophosphate in the deposition solution is 20-30 g/L, for example, 21 g/L, 22 g/L, 23 g/L, 24 g/L, 25 g/L, 26 g/L, 27 g/L, 28 g/L or 29 g/L, and the specific values therebetween are not exhaustive, and for the sake of brevity and brevity, the invention is not intended to be exhaustive of the specific values included in the scope.
Preferably, the concentration of tin pyrophosphate in the deposition solution is 0.01-0.5 g/L, and may be, for example, 0.03 g/L, 0.05 g/L, 0.07 g/L, 0.09 g/L, 0.1 g/L, 0.15 g/L, 0.2 g/L, 0.25 g/L, 0.3 g/L, 0.35 g/L, 0.4 g/L, or 0.45 g/L, and specific values therebetween, including space and simplicity, are not exhaustive and specific values included in the ranges are not recited herein.
Preferably, the concentration of potassium pyrophosphate in the deposition solution is 20-80 g/L, for example, 25 g/L, 30 g/L, 35 g/L, 40 g/L, 45 g/L, 50 g/L, 55 g/L, 60 g/L, 65 g/L, 70 g/L or 75 g/L, and the specific values therebetween are not exhaustive, and for the sake of brevity and clarity, the invention is not intended to include the specific values within the scope.
Preferably, the concentration of monopotassium phosphate in the deposition solution is 30-90 g/L, and may be, for example, 35 g/L, 40 g/L, 45 g/L, 50 g/L, 55 g/L, 60 g/L, 65 g/L, 70 g/L, 75 g/L, 80 g/L, or 85 g/L, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the current density of the electrochemical deposition is 1.0-1.5A/dm 2 For example, it may be 1.05A/dm 2 、1.1 A/dm 2 、1.15 A/dm 2 、1.2 A/dm 2 、1.25 A/dm 2 、1.3 A/dm 2 、1.35 A/dm 2 、1.4 A/dm 2 Or 1.45A/dm 2 And the specific values between the foregoing, are not intended to be exhaustive or to limit the invention to the precise values encompassed within the scope, for reasons of brevity and clarity.
Preferably, the deposition time of the electrochemical deposition is 5-15 min, for example, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min or 14 min, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the temperature of the electrochemical deposition is 20-30 ℃, for example, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃ or 29 ℃, and the specific values therebetween are limited for the sake of brevity and conciseness, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the tin-copper alloy layer has a thickness of 2 to 15 μm, and may be, for example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm or 14 μm, and specific values therebetween, which are not intended to be exhaustive for the invention and for the sake of brevity.
Preferably, the tin-copper alloy layer has a tin content of 0.01-0.5% by mass, which may be, for example, 0.03%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, or 0.45%, and specific values therebetween, which are not intended to be exhaustive for the sake of brevity and brevity.
As the preferred technical scheme of the invention, the metal grid line is the tin-copper alloy grid line formed by electrochemical deposition, so that the traditional screen printing silver grid line is replaced, and the manufacturing cost of the grid line is greatly reduced; on the other hand, the tin-copper alloy has excellent conductivity and stability, effectively avoids oxidation, and does not need silver protection on the outer layer.
Preferably, an anti-plating glue layer is arranged on the high polymer conductive film and then patterned to obtain a grid line pattern; electrochemically depositing a tin-copper alloy layer on the grid line pattern to form a metal grid line; and removing the residual plating resisting glue layer to obtain the heterojunction solar cell.
Preferably, the material of the plating-resistant glue layer is wax slurry and/or high-molecular plating-resistant glue.
As the preferable technical scheme of the invention, the material of the plating resist layer is wax slurry and/or polymer plating resist which is used as a mask, the cost is lower than that of the traditional photoresist, and the formed polymer plating resist layer and the substrate are easier to strip through a hot solvent.
Preferably, the plating-resistant glue layer is obtained by a drying method after coating, and the coating method comprises spraying, spin coating or brushing.
Preferably, the thickness (dry film thickness) of the anti-plating glue layer is 2-10 μm, for example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm or 9 μm, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
Preferably, the patterning method is laser etching.
Preferably, the method of removing comprises: soaking the rest of the anti-plating glue layer with water at 60-100 deg.C (such as 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C or 95 deg.C), and stripping off the rest of the anti-plating glue layer; preferably, the stripping is achieved by spraying.
Preferably, after the battery piece with the grid line pattern is cleaned, the step of electrochemical deposition is carried out.
Preferably, the cleaning agent is an acid solution, and more preferably a sulfuric acid solution.
Preferably, the acid solution (sulfuric acid solution) has a concentration of 2-8%, for example, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, or 7.5%, and specific values therebetween, including for brevity and clarity, are not exhaustive and are not included in the scope of the invention.
Preferably, the preparation method specifically comprises the following steps:
(1) soaking the silicon substrate with the transparent conductive layer in the monomer mixed solution for 5-20 min, drying, and performing heat treatment at 80-120 deg.C for 10-120 s to perform polymerization reaction to obtain a polymer conductive film with a thickness of 0.05-0.2 μm;
the monomer mixed solution comprises 3, 4-ethylenedioxythiophene, styrene sulfonic acid monomers, an emulsifier, an initiator and water; the concentration of 3, 4-ethylenedioxythiophene in the monomer mixed solution is 0.05-0.2 mol/L, the concentration of styrene sulfonic acid monomer is 0.1-0.3 mol/L, the concentration of emulsifier is 1.0-4.0 g/L, and the concentration of initiator is 0.001-0.1 g/L;
(2) arranging an anti-plating adhesive layer with the thickness of 2-10 mu m on the polymer conductive film obtained in the step (1), and patterning the anti-plating adhesive layer to obtain a grid line pattern;
(3) electrochemically depositing a tin-copper alloy layer on the grid line pattern high polymer conductive film obtained in the step (2) to form a metal grid line; removing the residual plating resistant adhesive layer to obtain the heterojunction solar cell;
the current density of the electrochemical deposition is 1.0-1.5A/dm 2 The temperature is 20-30 ℃, and the deposition time is 5-15 min; the deposition solution for electrochemical deposition comprises copper pyrophosphate, tin pyrophosphate, potassium dihydrogen phosphate and water, and the pH value of the deposition solution is 8.5-9.5.
In a second aspect, the present invention provides a heterojunction solar cell, comprising a silicon substrate and transparent conductive layers respectively disposed on two sides of the silicon substrate; a polymer conductive film and a metal grid line are sequentially arranged on the transparent conductive layer, and the metal grid line is a tin-copper alloy grid line; the heterojunction solar cell is prepared by the preparation method of the first aspect.
In a third aspect, the present invention provides a photovoltaic module comprising a heterojunction solar cell as described in the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the heterojunction solar cell, the electrochemical deposition process is used for replacing a low-temperature silver paste process, and the tin-copper alloy is used as the metal grid line, so that the manufacturing cost of the cell is remarkably reduced, the obtained metal grid line has better conductivity and stability, and an outer protective layer is not required to be arranged. As a process matched with electrochemical deposition, the preparation method adopts an in-situ polymerization mode to form a PEDOT (Poly ethylene glycol Ether), namely a PSS (Poly ethylene styrene) high-molecular conductive film which is used as a bonding layer of a transparent conductive layer and a metal grid line, can effectively improve the conductivity of the transparent conductive layer and increase the platability; meanwhile, the polymer conductive film can prevent the damage to TCO (transparent conductive oxide) during the preparation of a grid line pattern by laser etching, and prevent copper ions from migrating to the cell, so that the obtained heterojunction solar cell has higher open-circuit voltage and cell efficiency, the open-circuit voltage is greater than 718 mV, the cell efficiency is greater than 22.2%, and the comprehensive performance of the heterojunction solar cell is improved.
Drawings
FIG. 1 is a schematic structural diagram of a heterojunction solar cell according to example 1;
fig. 2 is a schematic structural view of an intermediate battery piece obtained in step (1) in the production method described in example 1;
fig. 3 is a schematic structural view of an intermediate battery piece obtained in step (2) of the production method described in example 1;
fig. 4 is a schematic structural view of an intermediate battery piece obtained in step (3) of the production method described in example 1;
fig. 5 is a schematic structural view of an intermediate battery piece obtained in step (4) of the production method described in example 1;
the transparent conductive film comprises a substrate 1, a substrate 2, a polymer conductive film 3, a metal grid line and a plating-resistant glue layer 4.
Detailed Description
It is to be understood that in the description of the present invention, the terms "upper", "lower", "side", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
It should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "provided", "disposed", "connected" and "connected" should be interpreted broadly, and may be, for example, a fixed connection, a detachable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the following embodiments of the present invention, the raw materials used are commercially available, and for example, the silicon substrate provided with the transparent conductive layer is a commercially available silicon substrate provided with transparent conductive layers (TCO films) on both sides, sodium styrene phenol polyoxyethylene ether sulfonate is obtained from haian petrochemical, and the polymer plating resist is an electroplating strippable protective glue obtained from saint coating of guangdong.
Example 1
A heterojunction solar cell and a preparation method thereof are provided, and the preparation method specifically comprises the following steps:
(1) mixing monomers (3, 4-ethylenedioxythiophene EDOT and styrene sulfonic acid), an emulsifier (sodium styrene phenol polyoxyethylene ether sulfonate and isooctyl alcohol sodium sulfate) and an initiator (sodium persulfate) with water to prepare a monomer mixed solution, wherein the concentration of EDOT is 0.1 mol/L, the concentration of styrene sulfonic acid is 0.2 mol/L, the concentration of sodium styrene phenol polyoxyethylene ether sulfonate is 2 g/L, the concentration of isooctyl alcohol sodium sulfate is 0.5 g/L, and the concentration of sodium persulfate is 0.01 g/L;
treating the surface of a silicon substrate provided with a transparent conductive layer (TCO film) with 5% dilute sulfuric acid for 2 min for activation, then soaking the silicon substrate in a monomer mixed solution for 5 min, taking out the silicon substrate, and carrying out heat treatment at 120 ℃ for 1 min to obtain a polymer conductive film with the film thickness of 0.05 mu m;
(2) spraying a layer of polymer plating resist on the polymer conductive film obtained in the step (1), and drying at 110 ℃ to obtain a plating resist layer with the thickness of 5 microns;
(3) carrying out graphical processing on the anti-plating adhesive layer obtained in the step (2), and obtaining a grid line graph by adopting laser etching;
(4) cleaning the battery piece with the grid line pattern obtained in the step (3) by using 5% sulfuric acid, and then performing electrochemical deposition on the tin-copper alloy at room temperature, wherein the deposition solution for electrochemical deposition is an aqueous solution containing 25 g/L of copper pyrophosphate, 0.1 g/L of tin pyrophosphate, 50 g/L of potassium pyrophosphate and 60 g/L of potassium dihydrogen phosphate, and the pH value of the aqueous solution is 9.0; the current density of the electrochemical deposition is 1.0A/dm 2 Depositing for 5 min to obtain a tin-copper alloy layer with the thickness of 3 mu m and form a metal grid line;
(5) and (4) soaking the cell sheet formed with the metal grid line in hot water at 80 ℃ for 30 s, and quickly removing the residual plating resistant adhesive layer by adopting a spraying mode to obtain the heterojunction solar cell.
A schematic structural diagram of the heterojunction solar cell in this embodiment is shown in fig. 1, and includes a silicon substrate 1 (specifically, including a silicon substrate and transparent conductive layers respectively disposed on two sides of the silicon substrate) with a transparent conductive layer, and a polymer conductive film 2 and a metal gate line 3 (a tin-copper alloy gate line) are sequentially disposed on the transparent conductive layer; in the preparation method of the heterojunction solar cell, the structural schematic diagrams of the intermediate cell obtained in the steps (1) to (4) are respectively shown in fig. 2, fig. 3, fig. 4 and fig. 5, wherein 1 represents a silicon substrate provided with a transparent conductive layer, 2 represents a high-molecular conductive film, 3 represents a metal grid line, and 4 represents an anti-plating glue layer; and (5) obtaining the heterojunction solar cell with the structure shown in the figure 1.
Example 2
A heterojunction solar cell and a preparation method thereof are provided, wherein the preparation method specifically comprises the following steps:
(1) mixing monomers (EDOT and styrene sulfonic acid), emulsifiers (sodium diphenylethylene phenol polyoxyethylene ether sulfonate and sodium isooctanolate sulfate), an initiator (sodium persulfate) and water to prepare a monomer mixed solution, wherein the concentration of EDOT is 0.1 mol/L, the concentration of styrene sulfonic acid is 0.2 mol/L, the concentration of sodium diphenylethylene phenol polyoxyethylene ether sulfonate is 2 g/L, the concentration of sodium isooctanolate sulfate is 0.5 g/L, and the concentration of sodium persulfate is 0.01 g/L;
treating the surface of a silicon substrate provided with a transparent conductive layer (TCO film) with 5% dilute sulfuric acid for 2 min for activation, then soaking the silicon substrate in a monomer mixed solution for 10 min, taking out the silicon substrate, and carrying out heat treatment at 120 ℃ for 1 min to obtain a polymer conductive film with the film thickness of 0.1 mu m;
(2) spraying a layer of polymer plating resist on the polymer conductive film obtained in the step (1), and drying at 110 ℃ to obtain a plating resist layer with the thickness of 5 microns;
(3) carrying out graphical processing on the anti-plating adhesive layer obtained in the step (2), and obtaining a grid line graph by adopting laser etching;
(4) cleaning the battery piece with the grid line pattern obtained in the step (3) by using 5% sulfuric acid, and then performing electrochemical deposition on the tin-copper alloy at room temperature, wherein the deposition solution for electrochemical deposition is an aqueous solution containing 25 g/L of copper pyrophosphate, 0.1 g/L of tin pyrophosphate, 50 g/L of potassium pyrophosphate and 60 g/L of potassium dihydrogen phosphate, and the pH value of the aqueous solution is 9.0; the current density of the electrochemical deposition is 1.5A/dm 2 Depositing for 5 min to obtain a tin-copper alloy layer with the thickness of 4.5 mu m and form a metal grid line;
(5) and (4) soaking the cell sheet formed with the metal grid line in hot water at 80 ℃ for 30 s, and quickly removing the residual plating resistant adhesive layer by adopting a spraying mode to obtain the heterojunction solar cell.
Example 3
A heterojunction solar cell and a preparation method thereof are provided, wherein the preparation method specifically comprises the following steps:
(1) mixing monomers (EDOT and styrene sulfonic acid), emulsifiers (sodium diphenylethylene phenol polyoxyethylene ether sulfonate and sodium isooctanolate sulfate), an initiator (sodium persulfate) and water to prepare a monomer mixed solution, wherein the concentration of EDOT is 0.1 mol/L, the concentration of styrene sulfonic acid is 0.2 mol/L, the concentration of sodium diphenylethylene phenol polyoxyethylene ether sulfonate is 2 g/L, the concentration of sodium isooctanolate sulfate is 0.5 g/L, and the concentration of sodium persulfate is 0.01 g/L;
treating the surface of a silicon substrate provided with a transparent conductive layer (TCO film) with 5% dilute sulfuric acid for 2 min for activation, then soaking the silicon substrate in a monomer mixed solution for 10 min, taking out the silicon substrate, and carrying out heat treatment at 120 ℃ for 1 min to obtain a polymer conductive film with the film thickness of 0.1 mu m;
(2) spraying a layer of polymer plating resist on the polymer conductive film obtained in the step (1), and drying at 110 ℃ to obtain a plating resist layer with the thickness of 10 microns;
(3) carrying out graphical processing on the anti-plating adhesive layer obtained in the step (2), and obtaining a grid line graph by adopting laser etching;
(4) cleaning the battery piece which is formed with the grid line pattern and obtained in the step (3) by using 5% sulfuric acid, and then carrying out electrochemical deposition on the tin-copper alloy at room temperature, wherein the deposition solution for electrochemical deposition is an aqueous solution containing 25 g/L of copper pyrophosphate, 0.1 g/L of tin pyrophosphate, 50 g/L of potassium pyrophosphate and 60 g/L of potassium dihydrogen phosphate, and the pH value of the aqueous solution is 9.0; the current density of the electrochemical deposition is 1.5A/dm 2 Depositing for 10 min to obtain a tin-copper alloy layer with the thickness of 10 mu m and form a metal grid line;
(5) and (4) soaking the cell sheet formed with the metal grid line in hot water at 80 ℃ for 30 s, and quickly removing the residual plating resistant adhesive layer by adopting a spraying mode to obtain the heterojunction solar cell.
Example 4
A heterojunction solar cell and a preparation method thereof are provided, wherein the preparation method specifically comprises the following steps:
(1) mixing monomers (EDOT and styrene sulfonic acid), emulsifiers (sodium diphenylethylene phenol polyoxyethylene ether sulfonate and sodium isooctanolate sulfate), an initiator (sodium persulfate) and water to prepare a monomer mixed solution, wherein the concentration of EDOT is 0.1 mol/L, the concentration of styrene sulfonic acid is 0.2 mol/L, the concentration of sodium diphenylethylene phenol polyoxyethylene ether sulfonate is 2 g/L, the concentration of sodium isooctanolate sulfate is 0.5 g/L, and the concentration of sodium persulfate is 0.01 g/L;
treating the surface of a silicon substrate provided with a transparent conductive layer (TCO film) with 5% dilute sulfuric acid for 2 min for activation, then soaking the silicon substrate in a monomer mixed solution for 8 min, taking out the silicon substrate, and carrying out heat treatment at 120 ℃ for 1 min to obtain a polymer conductive film with the film thickness of 0.08 mu m;
(2) spraying a layer of polymer plating resist on the polymer conductive film obtained in the step (1), and drying at 110 ℃ to obtain a plating resist layer with the thickness of 6 microns;
(3) carrying out graphical processing on the anti-plating adhesive layer obtained in the step (2), and obtaining a grid line graph by adopting laser etching;
(4) cleaning the battery piece with the grid line pattern obtained in the step (3) by using 5% sulfuric acid, and then performing electrochemical deposition on the tin-copper alloy at room temperature, wherein the deposition solution for electrochemical deposition is an aqueous solution containing 25 g/L of copper pyrophosphate, 0.1 g/L of tin pyrophosphate, 50 g/L of potassium pyrophosphate and 60 g/L of potassium dihydrogen phosphate, and the pH value of the aqueous solution is 9.0; the current density of the electrochemical deposition is 1.2A/dm 2 Depositing for 8 min to obtain a tin-copper alloy layer with the thickness of 6 mu m and form a metal grid line;
(5) and (4) soaking the cell sheet formed with the metal grid line in hot water at 80 ℃ for 30 s, and quickly removing the residual plating resistant adhesive layer by adopting a spraying mode to obtain the heterojunction solar cell.
Comparative example 1
A heterojunction solar cell and a preparation method thereof are provided, wherein the preparation method specifically comprises the following steps:
(1) the method comprises the following steps of (1) developing a grid line pattern on a silicon substrate provided with a transparent conducting layer (TCO film) by adopting PVD copper 80 nm as a seed layer (a combining layer) through film pasting and exposure;
(2) performing electrochemical deposition of a tin-copper alloy on the battery piece with the grid line pattern obtained in the step (1) at room temperature, wherein the deposition solution for electrochemical deposition is an aqueous solution containing 25 g/L of copper pyrophosphate, 0.1 g/L of tin pyrophosphate, 50 g/L of potassium pyrophosphate and 60 g/L of potassium dihydrogen phosphate, and the pH value of the aqueous solution is 9.0; the electrochemical depositionHas a current density of 1.2A/dm 2 Depositing for 8 min to obtain a tin-copper alloy layer with the thickness of 6 mu m and form a metal grid line;
(3) and (3) removing the film of the cell with the metal grid line formed in the step (2) by using a 5% KOH solution, and removing the seed layer (copper layer) by using a mixed solution containing 5% sulfuric acid and 5% hydrogen peroxide to obtain the heterojunction solar cell.
Comparative example 2
A heterojunction solar cell and a preparation method thereof are provided, wherein the preparation method specifically comprises the following steps:
(1) activating a silicon substrate provided with a transparent conductive layer (TCO film) by using 5% dilute sulfuric acid for 2 min, then coating a layer of PEDOT (PSS glue solution (purchased from Suzhou subfamily) on the TCO, and drying to obtain a high polymer conductive film with the film thickness of 0.5 mu m;
(2) spraying a layer of polymer plating resist on the polymer conductive film obtained in the step (1), and drying at 110 ℃ to obtain a plating resist layer with the thickness of 5 microns;
(3) carrying out graphical processing on the anti-plating adhesive layer obtained in the step (2), and obtaining a grid line graph by adopting laser etching;
(4) cleaning the battery piece with the grid line pattern obtained in the step (3) by using 5% sulfuric acid, and then performing electrochemical deposition on the tin-copper alloy at room temperature, wherein the deposition solution for electrochemical deposition is an aqueous solution containing 25 g/L of copper pyrophosphate, 0.1 g/L of tin pyrophosphate, 50 g/L of potassium pyrophosphate and 60 g/L of potassium dihydrogen phosphate, and the pH value of the aqueous solution is 9.0; the current density of the electrochemical deposition is 1.5A/dm 2 Depositing for 5 min to obtain a tin-copper alloy layer with the thickness of 4.5 mu m and form a metal grid line;
(5) and (4) soaking the cell sheet formed with the metal grid line in hot water at 80 ℃ for 30 s, and quickly removing the residual plating resistant adhesive layer by adopting a spraying mode to obtain the heterojunction solar cell.
And (3) performance testing:
using a Newport IV tester, the method according to IEC 60904 standard (Spectrum AM 1.5, light intensity 1000W/m) 2 Temperature 25 ℃ C.) test examples were conducted separately1-4, comparative examples 1-2, and open circuit voltage and cell efficiency were obtained as shown in table 1:
TABLE 1
The performance test data in table 1 show that the electrochemical deposition process is adopted to replace the low-temperature silver paste process, and the tin-copper alloy is used as the metal grid line, so that the manufacturing cost of the battery is remarkably reduced, the obtained metal grid line has better conductivity and stability, and an outer protective layer is not required to be arranged. As a process matched with electrochemical deposition, the preparation method adopts an in-situ polymerization mode to form a PEDOT (PSS) high-molecular conductive film which is used as a bonding layer of a transparent conductive layer and a metal grid line, can effectively improve the conductivity of the transparent conductive layer, increase the platability, prevent the damage to TCO when a grid line pattern is prepared by laser etching, and prevent copper ions from migrating to a cell, so that the open-circuit voltage of the obtained heterojunction solar cell is more than 718 mV, and the cell efficiency is more than 22.2%; compared with comparative example 1 in which a metal layer is used as a seed layer (bonding layer), the heterojunction solar cell provided by embodiments 1 to 4 of the present invention has higher open-circuit voltage and cell efficiency, and significantly improves the comprehensive performance of the heterojunction solar cell.
The invention takes EDOT and styrene sulfonic acid as monomers, and directly polymerizes in situ on a silicon substrate provided with a transparent conducting layer to form PEDOT with controllable thickness, namely PSS high polymer conducting film, which has obvious improvement effect on conductivity, platability and comprehensive performance of a battery; if a conventional physical coating method is adopted to prepare the PEDOT/PSS layer, the thickness of the obtained high-molecular conductive film is difficult to control, the film thickness is uneven, the physical coating method is difficult to control the thickness of the high-molecular conductive film to be 0.05-0.2 mu m, and the excessively thick PEDOT/PSS conductive layer increases the charge transfer resistance, influences the transparency of a cell piece and causes the performance reduction of the heterojunction solar cell.
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must be implemented by relying on the above process steps. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (9)
1. A method for fabricating a heterojunction solar cell, the method comprising: polymerizing a combination of 3, 4-ethylenedioxythiophene and styrene sulfonic acid monomers serving as monomers on a silicon substrate provided with a transparent conductive layer to obtain a polymer conductive film; arranging an anti-plating glue layer on the high polymer conductive film and then patterning to obtain a grid line pattern; electrochemically depositing a tin-copper alloy layer on the grid line pattern to form a metal grid line; and removing the residual plating resisting glue layer to obtain the heterojunction solar cell.
2. The preparation method of claim 1, wherein the molar ratio of the 3, 4-ethylenedioxythiophene to the styrene sulfonic acid monomer is 1 (0.5-4); the thickness of the polymer conductive film is 0.05-0.2 μm.
3. The method of claim 1 or 2, wherein the polymerization process comprises: soaking the silicon substrate provided with the transparent conducting layer in the monomer mixed solution, and then carrying out heat treatment at 70-120 ℃ for 10-120 s to carry out reaction to obtain the polymer conducting film;
the monomer mixed solution comprises a monomer, an emulsifier, an initiator and water; the concentration of the monomer in the monomer mixed solution is 0.1-0.5 mol/L, and the concentration of the emulsifier is 1.0-4.0 g/L.
4. The production method according to claim 1, wherein the silicon substrate provided with the transparent conductive layer is a surface-treated silicon substrate provided with a transparent conductive layer, the surface-treatment agent is an acid solution, and the surface treatment time is 1 to 30 min.
5. The preparation method according to claim 1, characterized in that the deposition solution for electrochemical deposition comprises copper pyrophosphate, tin pyrophosphate, potassium dihydrogen phosphate and water, and the pH value of the deposition solution is 8.5-9.5;
the current density of the electrochemical deposition is 1.0-1.5A/dm 2 The deposition time is 5-15 min, and the temperature is 20-30 ℃.
6. The production method according to claim 1 or 5, wherein the tin-copper alloy layer has a thickness of 2 to 15 μm; the mass percentage of tin in the tin-copper alloy layer is 0.01-0.5%.
7. The preparation method according to claim 1, characterized in that the preparation method comprises the following steps:
(1) soaking the silicon substrate with the transparent conductive layer in the monomer mixed solution for 5-20 min, drying, and performing heat treatment at 70-120 deg.C for 10-120 s to perform polymerization reaction to obtain a polymer conductive film with a thickness of 0.05-0.2 μm;
the monomer mixed solution comprises 3, 4-ethylenedioxythiophene, styrene sulfonic acid monomers, an emulsifier, an initiator and water; the concentration of 3, 4-ethylenedioxythiophene in the monomer mixed solution is 0.05-0.2 mol/L, the concentration of styrene sulfonic acid monomer is 0.1-0.3 mol/L, the concentration of emulsifier is 1.0-4.0 g/L, and the concentration of initiator is 0.001-0.1 g/L;
(2) arranging an anti-plating adhesive layer with the thickness of 2-10 mu m on the polymer conductive film obtained in the step (1), and patterning the anti-plating adhesive layer to obtain a grid line pattern;
(3) electrochemically depositing a tin-copper alloy layer on the grid line pattern high polymer conductive film obtained in the step (2) to form a metal grid line; removing the residual plating resistant adhesive layer to obtain the heterojunction solar cell;
the current density of the electrochemical deposition is 1.0-1.5A/dm 2 The temperature is 20-30 ℃, and the deposition time is 5-15 min; the deposition solution for electrochemical deposition comprises copper pyrophosphate, tin pyrophosphate, potassium dihydrogen phosphate and water, and the pH value of the deposition solution is 8.5-9.5.
8. The heterojunction solar cell is characterized by comprising a silicon substrate and transparent conducting layers respectively arranged on two sides of the silicon substrate; a polymer conductive film and a metal grid line are sequentially arranged on the transparent conductive layer, and the metal grid line is a tin-copper alloy grid line;
the heterojunction solar cell is prepared by the preparation method according to any one of claims 1 to 7.
9. A photovoltaic module comprising the heterojunction solar cell of claim 8.
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