CN113851559A - Preparation method of TOPCon battery - Google Patents

Preparation method of TOPCon battery Download PDF

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Publication number
CN113851559A
CN113851559A CN202111263015.3A CN202111263015A CN113851559A CN 113851559 A CN113851559 A CN 113851559A CN 202111263015 A CN202111263015 A CN 202111263015A CN 113851559 A CN113851559 A CN 113851559A
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silicon wafer
amorphous silicon
annealing
silicon
coating
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CN113851559B (en
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任常瑞
李金�
张佳舟
蒋韦
董建文
符黎明
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Changzhou Shichuang Energy Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1864Annealing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1872Recrystallisation
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/547Monocrystalline silicon PV cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention discloses a preparation method of a TOPCon battery, which comprises the steps of preparing a tunneling oxide layer on the back surface of a silicon wafer by LPCVD (low pressure chemical vapor deposition), depositing intrinsic amorphous silicon, removing amorphous silicon on the front surface of the silicon wafer for plating, coating a liquid dopant on the back surface of the silicon wafer, drying, annealing the silicon wafer, crystallizing the amorphous silicon by annealing and activating impurities. The method can realize single-side diffusion without diffusion, is a process scheme for preparing an n + POLO structure, meets the high-yield requirement, optimizes a process window, avoids the risk of diffusion, can realize the removal of amorphous silicon before annealing for plating, simplifies the process steps, protects the front structure of the silicon wafer, improves the process controllability, and can solve the contradiction between the diffusion concentration and the tunneling layer effect.

Description

Preparation method of TOPCon battery
Technical Field
The invention relates to the field of photovoltaics, in particular to a preparation method of a TOPCon battery.
Background
In order to improve the proportion of photovoltaic power generation, cost reduction and efficiency improvement are two major lines of photovoltaic manufacturing, the current mainstream photovoltaic cell is a crystalline silicon solar cell, the TOPCon technology becomes one of the most potential novel high-efficiency cell technologies due to the extremely high compatibility of the process route and the traditional PERC cell production line and the obvious efficiency gain, and the related research is increased day by day.
With the development and introduction of TOPCon battery technology, the conversion efficiency of industrialized n-type TOPCon batteries exceeds 24%. The preparation of an n + POLO structure is the core technology of the battery, and the conventional preparation schemes in the industry at present have two types: firstly, thermal oxidation, LPCVD in-situ doping and high-temperature annealing; ② thermal oxygen + LPCVD intrinsic deposition + diffusion doping. The intrinsic poly Si deposition rate adopted in the scheme II is far higher than that of in-situ deposition, the LPCVD process time can be effectively reduced, the in-situ deposition can provide a more excellent doping curve and a larger tunneling oxygen layer process window, and compared with the traditional PERC cell, the complexity and the process time of the whole process are increased by the two schemes, so that the corresponding manufacturing cost is increased. How to continue to improve the conversion efficiency of the photovoltaic cell and reduce the process flow time so as to reduce the manufacturing cost is a common goal and direction in the photovoltaic industry.
The current technological process of the TOPCon battery mainly comprises the following steps:
the scheme is as follows: alkali texturing → boron diffusion → BSG removal on the back, alkali polishing on the back → tunneling oxygen + N + amorphous silicon deposition → front surface unwinding and plating → annealing → front and back surface plating → printed electrode sintering;
scheme II: alkali texturing → boron diffusion → back surface BSG removal, back surface alkali polishing → tunneling oxygen + intrinsic amorphous silicon deposition → phosphorus diffusion → front surface PSG removal → front surface wraparound plating → front and back surface plating → printed electrode, and sintering.
In the preparation aspect of the POLO structure, because the intrinsic deposition rate is far higher than that of in-situ deposition, the yield advantage is obvious by the same Poly Si thickness scheme, the first scheme adopts annealing for crystallization, the crystallization process is simple and controllable, the winding plating removal treatment can be carried out before crystallization without considering the winding expansion risk, the process steps are reduced, the front structure is free of etching risk (BSG protection) in the alkali polishing process, and the two schemes have defects in yield and process controllability respectively.
Disclosure of Invention
The invention aims to provide a preparation method of a TOPCon battery, which comprises the steps of preparing a tunneling oxide layer on the back surface of a silicon wafer by LPCVD (low pressure chemical vapor deposition), depositing intrinsic amorphous silicon, removing amorphous silicon on the front surface of the silicon wafer for coil plating, coating a liquid dopant on the back surface of the silicon wafer, drying, annealing the silicon wafer, crystallizing the amorphous silicon by annealing and activating impurities.
Preferably, the preparation method of the TOPCon battery comprises the following specific steps:
1) cleaning a silicon wafer and texturing;
2) b diffusion;
3) removing the BSG on the back;
4) carrying out alkali polishing on the back surface;
5) preparing a tunneling oxide layer and depositing intrinsic amorphous silicon by back LPCVD;
6) removing the amorphous silicon plating on the front surface;
7) coating liquid dopant on the back and drying;
8) annealing to crystallize the amorphous silicon and activate the impurities;
9) coating the film on the front surface and the back surface;
10) printing an electrode;
11) and (5) sintering.
Preferably, in the step 6), the front amorphous silicon spin coating is removed by chain type alkali polishing.
Preferably, in step 7), the front side of the silicon wafer is placed on the support plate, and then the back side of the silicon wafer is coated with the liquid dopant.
Preferably, the support plate has an adsorption function, and the silicon wafer is fixed on the support plate through negative pressure adsorption.
Preferably, the coating is spin coating, roll coating or spray coating.
Preferably, the liquid dopant contains a group v element.
Preferably, the group V element is selected from one or more of N, P, As, Sb and Bi.
Preferably, the carrier plate has a heating function, and the dopant is dried by heating the carrier plate.
Preferably, in step 8), the annealing is carried out in a tube furnace or a chain furnace.
Preferably, in the step 8), the annealing process conditions are as follows: high temperature of 700-900 ℃ for 3-20 min, normal pressure and nitrogen atmosphere.
The invention has the advantages and beneficial effects that: after depositing intrinsic amorphous silicon by LPCVD, adopting a scheme of single-side dopant coating and annealing to realize crystallization and single-side diffusion of a-Si, completing preparation of n + Poly Si and forming an n + POLO structure; the method can realize single-side diffusion without diffusion, is a process scheme for preparing an n + POLO structure, meets the high-yield requirement, optimizes a process window, avoids the risk of diffusion, can realize the removal of amorphous silicon before annealing for plating, simplifies the process steps, protects the front structure of the silicon wafer, improves the process controllability, and can solve the contradiction between the diffusion concentration and the tunneling layer effect.
The invention has the following characteristics:
1. in the prior art, after a-Si is deposited by LPCVD, an n + POLO structure is prepared by high-temperature phosphorus diffusion (gas phase diffusion), the thickness of a tunneling oxide layer is only 1-2 nm, the diffusion process needs to simultaneously meet the concentration requirement and the tunneling effect of the oxide layer, the process window is small, and the fault tolerance rate is poor. The invention can freely control the doping concentration by preparing the solution of the liquid dopant and control the degree of the inner diffusion of the crystallization and oxidation layer by the annealing process, thereby realizing the enhancement of the process controllability.
2. In the prior art, gas phase diffusion is adopted for phosphorus diffusion, the risk of diffusion cannot be avoided, only the front HF-removing PSG is carried out after diffusion, then the front-side plating-removing process is completed, the process complexity is increased, HF possibly causes etching of the BSG in a non-plating-removing area, and then the risk of damaging the front-side suede exists in the alkali-washing plating-removing process. According to the invention, the introduction of doping elements on the back side of the silicon wafer is carried out by coating a liquid dopant on a single side, the front side of the silicon wafer is adsorbed and shielded by the carrier plate, the risk of the dopant being coated on the front side of the silicon wafer in a winding manner is avoided, the carrier plate has a heating function, the coating and drying can be completed and the curing is completed in one step, then the crystallization and the doping of phosphorus atoms (the impurity propulsion and the activation) are carried out by adopting an annealing manner, the front side is protected by the barrier layer BSG with the thickness of 50-120 nm, and the diffusion speed of the phosphorus atoms in the barrier layer BSG is very low, so that the phosphorus atoms cannot penetrate through the barrier layer BSG to be wound and expanded to the front side within the annealing time of 3-20 min, the risk of the winding and expansion is avoided, the winding and the plating can be directly removed before the annealing, the process flow is greatly simplified, and the texture structure of the front side is protected.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The invention provides a preparation method of a TOPCon battery, which comprises the following specific steps:
1) cleaning a silicon wafer and texturing;
2) b diffusion;
3) removing the BSG on the back;
4) carrying out alkali polishing on the back surface;
5) preparing a tunneling oxide layer and depositing intrinsic amorphous silicon by back LPCVD;
6) removing amorphous silicon on the front surface by chain type alkali throwing;
7) coating liquid dopant on the back and drying: the front surface of the silicon wafer can be flatly placed on a support plate with a negative pressure adsorption function and a heating function, the silicon wafer is fixed on the support plate through negative pressure adsorption, then a liquid dopant containing a V-group element (the V-group element is selected from one or more of N, P, As, Sb and Bi) is coated on the back surface of the silicon wafer, and then the dopant is dried through heating the support plate; the coating can adopt a spin coating, roll coating or spray coating mode;
8) annealing: annealing the silicon wafer in a tube furnace or a chain furnace to crystallize amorphous silicon and promote and activate impurities (one or more of N, P, As, Sb and Bi); the annealing process conditions are as follows: high temperature of 700-900 ℃ for 3-20 min, normal pressure and nitrogen atmosphere;
9) coating the film on the front surface and the back surface;
10) printing an electrode;
11) and (5) sintering.
The specific implementation case of the invention on the n-type TOPCon battery is as follows:
selecting an n-type monocrystalline silicon wafer with the resistivity range of 0.8-1.5 ohm.cm and the minority carrier lifetime of more than 2.5 ms, wherein the thickness is 170 mu m, and the size is 166 mm;
in KOH and H2O2Removing a damaged layer on the surface of the silicon wafer in the mixed solution, and then performing texturing in a KOH solution to form a pyramid textured surface on the surface of the silicon wafer, wherein the size of the pyramid textured surface is controlled to be 1-5 mu m;
after the texture surface is finished, preparing an emitter on the front side of the silicon wafer by adopting B diffusion, wherein the sheet resistance is 110-150 ohm.cm, the BSG thickness on the front side is 50-120 nm, and alkali polishing is carried out after BSG on the back side of the silicon wafer is removed, so that the reflectivity of the back side of the silicon wafer is more than 40%;
preparing a tunneling layer (1-2 nm) + a-Si (100-150 nm) on one side of an alkali polished surface (the back surface of a silicon wafer) in LPCVD (low pressure chemical vapor deposition), and removing amorphous silicon spiral coating (BSG as a barrier layer) on the front side by alkali washing after amorphous silicon deposition is completed;
then flatly placing the front side of the silicon wafer on a carrier plate, rolling and coating a liquid dopant containing P on the back side of the silicon wafer, and drying at 100-200 ℃ for 10-120 s;
then annealing in a tube furnace to crystallize the amorphous silicon and drive in and activate the impurity (P), wherein the annealing process conditions are as follows: high temperature of 700-900 ℃ for 3-20 min, normal pressure and nitrogen atmosphere;
depositing aluminum oxide with the thickness of 3-10 nm on the front side of the silicon wafer by using ALD, and preparing silicon nitride with the thickness of 75-80 nm by using PECVD; depositing silicon nitride with the thickness of 70-100 nm on the back of the silicon wafer to finish the preparation of a battery precursor;
and after the surface passivation is finished, metallizing the front side and the back side of the silicon chip, printing a silver paste electrode on the back side of the silicon chip and printing a silver aluminum paste electrode on the front side of the silicon chip in sequence in a screen printing mode, and sintering to finish the preparation of the battery.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a TOPCon battery is characterized in that after a tunneling oxide layer is prepared on the back surface of a silicon wafer through LPCVD and intrinsic amorphous silicon is deposited, amorphous silicon on the front surface of the silicon wafer is removed, winding plating is conducted, then liquid dopant is coated on the back surface of the silicon wafer and dried, then annealing is conducted on the silicon wafer, and the amorphous silicon is crystallized through annealing and impurities are activated.
2. The method of claim 1, wherein the method comprises the steps of:
1) cleaning a silicon wafer and texturing;
2) b diffusion;
3) removing the BSG on the back;
4) carrying out alkali polishing on the back surface;
5) preparing a tunneling oxide layer and depositing intrinsic amorphous silicon by back LPCVD;
6) removing the amorphous silicon plating on the front surface;
7) coating liquid dopant on the back and drying;
8) annealing to crystallize the amorphous silicon and activate the impurities;
9) coating the film on the front surface and the back surface;
10) printing an electrode;
11) and (5) sintering.
3. A method of fabricating a TOPCon cell as recited in claim 2 wherein in step 6) the front side amorphous silicon spin coating is removed using a chain type alkaline polish.
4. A topocon cell manufacturing method as claimed in claim 3, wherein in step 7), the front side of the silicon wafer is first laid flat on the carrier plate, and then the back side of the silicon wafer is coated with the liquid dopant.
5. The method of claim 4, wherein the carrier plate has an adsorption function, and the silicon wafer is fixed on the carrier plate by negative pressure adsorption.
6. The method of claim 4, wherein the coating is spin, roll or spray coating.
7. The method of claim 4, wherein the liquid dopant comprises a group V element.
8. The method of claim 4, wherein the carrier plate has a heating function, and the dopant is dried by heating the carrier plate.
9. A method of manufacturing a TOPCon cell according to claim 2, characterized in that in step 8) the annealing is performed in a tube furnace or a chain furnace.
10. The method for preparing a TOPCon battery as claimed in claim 2, wherein the annealing in step 8) is performed under the following process conditions: high temperature of 700-900 ℃ for 3-20 min, normal pressure and nitrogen atmosphere.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114709275A (en) * 2022-03-24 2022-07-05 江苏日托光伏科技股份有限公司 Preparation method of MWT-TOPCon battery
CN115020534A (en) * 2022-04-30 2022-09-06 常州时创能源股份有限公司 Preparation method of back-side graphical N region of IBC battery
CN115020535A (en) * 2022-04-30 2022-09-06 常州时创能源股份有限公司 Preparation method of back double-POLO structure of IBC battery
CN115101627A (en) * 2022-07-08 2022-09-23 三一集团有限公司 Double-sided passivation contact solar cell and preparation method thereof
CN116613245A (en) * 2023-06-09 2023-08-18 无锡松煜科技有限公司 Method for improving LPCVD (low pressure chemical vapor deposition) through rate of TOPCon battery

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CN206931575U (en) * 2017-06-15 2018-01-26 常州亿晶光电科技有限公司 The silicon chip support plate of plated film on solar cell
CN111668345A (en) * 2020-06-29 2020-09-15 浙江晶科能源有限公司 Solar cell and preparation method thereof
CN111785809A (en) * 2020-07-15 2020-10-16 常州时创能源股份有限公司 Method for preparing passivated contact cell
CN112359348A (en) * 2020-10-22 2021-02-12 江苏杰太光电技术有限公司 Method and device for depositing doped amorphous silicon thin film without winding plating
CN213327796U (en) * 2020-09-07 2021-06-01 黄河水电光伏产业技术有限公司 Mask plate
CN112885925A (en) * 2021-02-05 2021-06-01 泰州隆基乐叶光伏科技有限公司 Solar cell and manufacturing method thereof
CN214193440U (en) * 2020-11-26 2021-09-14 常州亿晶光电科技有限公司 Silicon wafer carrier plate for coating film on solar cell

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Publication number Priority date Publication date Assignee Title
CN206931575U (en) * 2017-06-15 2018-01-26 常州亿晶光电科技有限公司 The silicon chip support plate of plated film on solar cell
CN111668345A (en) * 2020-06-29 2020-09-15 浙江晶科能源有限公司 Solar cell and preparation method thereof
CN111785809A (en) * 2020-07-15 2020-10-16 常州时创能源股份有限公司 Method for preparing passivated contact cell
CN213327796U (en) * 2020-09-07 2021-06-01 黄河水电光伏产业技术有限公司 Mask plate
CN112359348A (en) * 2020-10-22 2021-02-12 江苏杰太光电技术有限公司 Method and device for depositing doped amorphous silicon thin film without winding plating
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114709275A (en) * 2022-03-24 2022-07-05 江苏日托光伏科技股份有限公司 Preparation method of MWT-TOPCon battery
CN115020534A (en) * 2022-04-30 2022-09-06 常州时创能源股份有限公司 Preparation method of back-side graphical N region of IBC battery
CN115020535A (en) * 2022-04-30 2022-09-06 常州时创能源股份有限公司 Preparation method of back double-POLO structure of IBC battery
CN115101627A (en) * 2022-07-08 2022-09-23 三一集团有限公司 Double-sided passivation contact solar cell and preparation method thereof
CN116613245A (en) * 2023-06-09 2023-08-18 无锡松煜科技有限公司 Method for improving LPCVD (low pressure chemical vapor deposition) through rate of TOPCon battery

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