WO2024120129A1 - Boron-diffusion selective emitter preparation method for topcon battery, and battery preparation process - Google Patents

Boron-diffusion selective emitter preparation method for topcon battery, and battery preparation process Download PDF

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WO2024120129A1
WO2024120129A1 PCT/CN2023/131449 CN2023131449W WO2024120129A1 WO 2024120129 A1 WO2024120129 A1 WO 2024120129A1 CN 2023131449 W CN2023131449 W CN 2023131449W WO 2024120129 A1 WO2024120129 A1 WO 2024120129A1
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boron
silicon wafer
expansion
diffusion
battery
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任常瑞
董建文
符黎明
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常州时创能源股份有限公司
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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
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • 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
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • 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
    • 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

Definitions

  • the invention relates to the technical field of equipment, and in particular to a method for preparing a boron-diffused selective emitter of a TOPCon battery and a battery preparation process.
  • the relatively mature boron SE scheme is mainly the secondary diffusion scheme; the first boron diffusion (light diffusion) - laser removal of local BSG (heavy diffusion area) - heavy diffusion (the light diffusion area is blocked by BSG, so as to achieve local heavy doping to complete the SE structure); the existing relatively mature technology is mainly the secondary diffusion scheme, 1.
  • the two boron diffusions have a great impact on the production capacity, and multiple high-temperature diffusions affect the quality of the matrix, resulting in the loss of the final battery efficiency; 2.
  • This scheme has very high requirements for laser (lossless film opening is required), which increases the equipment cost; 3.
  • There is interference between the two boron diffusion processes both are high-temperature processes, and the second boron diffusion will affect the light diffusion curve).
  • the object of the present invention is to provide a method for preparing a boron-diffused selective emitter of a TOPCon battery and a battery preparation process to solve the problems raised in the above-mentioned background technology.
  • the present invention provides the following technical solutions:
  • a method for preparing a boron-diffused selective emitter of a TOPCon cell comprises the following steps:
  • the front side of the silicon wafer texturing sample or the front side of the boron expansion is formed with a mask layer that can block the boron expansion;
  • Boron diffusion is performed on the front side of the silicon wafer. Boron emitter diffusion areas with different properties obtain different diffusion effects, forming a selective boron diffusion SE structure.
  • the present invention further proposes a method for preparing a single boron diffusion selective emitter of a TOPCon cell, comprising the following steps:
  • Step 1 forming a mask layer capable of blocking boron diffusion on the front side of the texturing sample by coating, deposition, printing or transfer;
  • Step 2 using laser to locally heat the target area of silicon wafer re-expansion, so that after the mask layer of the target area of silicon wafer re-expansion is modified or ablated by high-temperature heating, it no longer blocks the boron expansion to form a re-expansion area, and the remaining is a light expansion area, forming a boron emitter boron expansion area with different boron expansion properties;
  • Step 3 perform a single boron expansion on the above silicon wafer.
  • the boron emitter boron expansion regions with different boron expansion properties form light expansion areas and heavy expansion areas, forming a boron expansion selective emitter SE structure.
  • the present invention further proposes a battery preparation process based on the above-mentioned boron diffusion selective emitter preparation method and combined with de-wrap plating and reverse etching, comprising the following steps:
  • Step 1 Silicon wafer texturing and front side boron expansion and re-expansion
  • Step 2 Alkaline polishing of silicon wafer and removal of BSG on the front side;
  • Step 3 Forming an alkali-resistant mask layer on the front side of the silicon wafer that can be modified by low-power laser and can block boron diffusion;
  • Step 4 Use a low-power laser to modify the mask layer in the lightly doped area on the front side of the silicon wafer, so that the mask layer in this area is no longer alkali-resistant or is directly ablated or evaporated;
  • Step 5 Prepare a tunneling layer and amorphous silicon intrinsic deposition on the back of the silicon wafer, and perform high-temperature phosphorus diffusion;
  • Step 6 Use low-temperature texturing process to remove the front side plating and realize light doping reverse etching to realize boron SE structure; then deposit aluminum oxide layer and silicon nitride layer on both sides of the silicon wafer;
  • Step 7 Surface treatment of silicon wafer: printing silver paste electrode on the back of silicon wafer and silver aluminum paste electrode on the front, and then sintering to complete battery preparation.
  • the silicon wafer texture is prepared in advance before the step one, the damaged layer on the surface of the silicon wafer is removed in a mixed solution of KOH and H2O2, and then the texture is made in a KOH solution to form a pyramid texture on the surface, and the size of the pyramid texture is controlled to be 1-5 ⁇ m; in the step one, the emitter is prepared by boron diffusion and re-diffusion on the front side of the silicon wafer, and its square resistance is 50-100 ohm/ ⁇ ; the BSG thickness is 50-120 nm; in the step two, the back side of the silicon wafer is alkaline polished after the BSG is removed, so that the reflectivity of the back side of the silicon wafer is greater than 40%, and HF is used to remove the BSG on the front side after the alkaline polishing.
  • the mask layer in step three is a solid non-metallic compound mixed slurry
  • the solute includes non-metallic oxides, sulfides, nitrides, phosphides and/or arsenides
  • the solvent includes water, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and/or triethanolamine.
  • the alkali-resistant mask layer in step three is formed by any one of coating, deposition, printing and transfer; the printing method uses a 400-500 mesh, 7-15 ⁇ m line diameter full-opening screen.
  • the low-power laser modification treatment in step 4 is to use a nanosecond low-power laser with a wavelength of 300-500nm, a power of 20-40W, a large spot size of 50-200 ⁇ m, and a line scanning method to perform local heating or film opening treatment corresponding to the grid line design pattern.
  • a tunneling layer of 1-2 nm and an amorphous silicon intrinsic deposition of 50-150 nm are prepared on the back side of the silicon wafer in LPCVD, and high-temperature phosphorus diffusion is adopted with a diffusion temperature of 700-900° C. to complete high-temperature crystallization and diffusion.
  • the square resistance of the lightly doped reverse etch is 130-300 ohm/ ⁇ , 3-10nm thick aluminum oxide is deposited on both sides of the silicon wafer using ALD, and 75-80nm thick silicon nitride is prepared using PECVD, and 70-100nm thick silicon nitride is deposited on the back of the silicon wafer.
  • step seven metallization is performed on the front and back of the silicon wafer, and silver paste electrodes are printed on the back of the silicon wafer and silver aluminum paste electrodes are printed on the front in sequence by screen printing, and then sintering is performed to complete the battery preparation.
  • the present invention creatively proposes a method for preparing a selective emitter for boron diffusion based on a single laser, which effectively improves production capacity.
  • the mask can be prepared by coating, deposition, printing or transfer, etc. The key point is that the mask can block a certain degree of boron diffusion, and after high-temperature heating, it is modified to no longer be alkali-resistant or no longer block boron diffusion.
  • the laser can use a nanosecond low-power laser, which is low-cost and easy to control.
  • the de-wrap plating adopts a low-temperature velvet process to protect the front velvet surface while realizing the two functions of de-poly wrap plating and light doping reverse engraving, with a high yield rate.
  • FIG. 1 is a simplified flow chart of a method for preparing a boron-diffused selective emitter of a TOPCon cell.
  • FIG. 2 is a simplified flow chart of a method for preparing a single boron diffusion selective emitter of a TOPCon cell.
  • FIG3 is a simplified flow chart of a battery preparation process based on boron diffusion selective emitter preparation combined with de-wrap plating and reverse etching.
  • N-type TOPCon batteries N-type TOPCon batteries
  • a method for preparing a boron-diffused selective emitter of a TOPCon cell includes the following steps:
  • Step 1 deposit a mask layer (which can block a certain degree of boron diffusion) on the front of the texturing sample by coating, deposition, printing or transfer;
  • the mask layer is a solid non-metallic compound mixed slurry that can block boron diffusion
  • the solute includes non-metallic oxides, sulfides, nitrides, phosphides and/or arsenides
  • the solvent includes water, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and/or triethanolamine;
  • Step 2 Use laser for local heating. After high temperature heating and modification, the mask no longer blocks boron diffusion.
  • Step 3 Single boron expansion.
  • the unheated mask blocking area is the light expansion area
  • the heated and modified mask area is the heavy expansion area, forming a boron-expanded selective emitter SE structure.
  • a TOPCon battery preparation process for boron-diffused selective emitter preparation combined with de-wrap plating and reverse etching including the following steps; select N-type single crystal silicon wafers with a resistivity range of 0.8ohm.cm and a minority carrier lifetime of >2.5 ms, a thickness of 170 ⁇ m, and a size of 210mm.
  • the damaged layer on the surface of the silicon wafer is removed in a mixed solution of KOH and H 2 O 2 , and then texturing is carried out in the KOH solution to form a pyramid velvet surface on the surface.
  • the size of the pyramid velvet surface is controlled to be 3 ⁇ m.
  • the emitter is prepared on the front side of the silicon wafer using the B diffusion re-expansion process (square resistance 70 ohm/ ⁇ ), the BSG thickness is 80nm, and the back side of the silicon wafer is alkaline polished after removing the BSG to make the reflectivity of the back side of the silicon wafer greater than 40%.
  • HF is used to remove the BSG on the front side;
  • a mask layer is deposited on the front of the sample by transfer printing as an alkali-resistant barrier layer; laser is used for local heating (lightly doped area), and the mask is no longer alkali-resistant after high-temperature heating modification;
  • the mask layer is a type of solid non-metallic compound mixed slurry that can block boron diffusion, the solute includes non-metallic oxides, sulfides, nitrides, phosphides and/or arsenides, and the solvent includes water, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and/or triethanolamine;
  • a 2nm tunneling layer + 100nm amorphous silicon intrinsic deposition is prepared on one side in LPCVD, and high-temperature crystallization and diffusion are completed using high-temperature phosphorus diffusion at a temperature of 800°C;
  • a low-temperature texturing process is used to remove the front-side plating and achieve light-doped reverse etching (obtaining a light-doped square resistivity of 200 ohm/ ⁇ ).
  • ALD is then used to deposit 6nm thick aluminum oxide on both sides of the silicon wafer, and PECVD is used to prepare 75nm thick silicon nitride; 70nm thick silicon nitride is deposited on the back of the silicon wafer to complete the preparation of the battery precursor.
  • metallization is performed on the front and back of the silicon wafer.
  • Silver paste electrodes are printed on the back of the silicon wafer and silver aluminum paste electrodes are printed on the front by screen printing, and then sintering is performed to complete the battery preparation.

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Abstract

A boron-diffusion selective emitter (SE) preparation method for a TOPCon battery, and a battery preparation process, which belong to the technical field of battery preparation. The method comprises the following steps: S1, forming a mask layer, which can block boron diffusion, on the front face of a silicon wafer texturing sample or on a heavy-boron-diffusion front face; S2, performing modification or ablation treatment on a mask layer in a target heavy-diffusion region of a silicon wafer, so as to form boron emitter boron diffusion regions having different boron diffusion properties; and S3, performing boron diffusion on the front face of the silicon wafer, such that the boron emitter boron diffusion regions having different properties obtain different diffusion effects, thereby forming a selective boron diffusion SE structure.

Description

一种TOPCon电池的硼扩选择性发射极制备方法及电池制备工艺A method for preparing a boron-diffused selective emitter of a TOPCon battery and a battery preparation process 技术领域Technical Field
本发明涉及设备技术领域，具体是一种TOPCon电池的硼扩选择性发射极制备方法及电池制备工艺。The invention relates to the technical field of equipment, and in particular to a method for preparing a boron-diffused selective emitter of a TOPCon battery and a battery preparation process.
背景技术Background technique
为提高光伏发电的比例，降本和提效是光伏制造的两大主线，目前晶体硅太阳能电池依然占据光伏电池的主要市场，而TOPCon技术由于其工艺路线与传统PERC电池产线极高的兼容性以及其明显的效率增益（目前报道量产效率>24%），成为目前最有潜力的新型高效电池技术之一。TOPCon电池正面采用硼扩制备发射极，而选择性发射极（SE）技术的叠加是目前其正面复合下降，电池效率提升主要手段之一；目前行业主要硼SE量产方案。In order to increase the proportion of photovoltaic power generation, cost reduction and efficiency improvement are the two main lines of photovoltaic manufacturing. At present, crystalline silicon solar cells still occupy the main market of photovoltaic cells, and TOPCon technology has become one of the most promising new high-efficiency battery technologies due to its process route and the high compatibility with the traditional PERC battery production line and its obvious efficiency gain (currently reported mass production efficiency>24%). The front of the TOPCon battery uses boron expansion to prepare the emitter, and the superposition of selective emitter (SE) technology is currently one of the main means to reduce its front recombination and improve battery efficiency; the current industry's main boron SE mass production plan.
目前相对成熟的硼SE方案主要为二次扩散方案；初次硼扩（轻扩）-激光去除局部BSG（重扩区域）-进行重扩（轻扩区有BSG阻挡，从而实现局部重掺完成SE结构）；现有较成熟的技术主要为二次扩散的方案，1、两次硼扩对产能影响很大，且多次高温扩散影响基体质量导致最终电池效率受损；2、该方案对激光要求很高（需进行无损开膜）增加了设备成本；3、两次硼扩工艺之间存在干涉影响（均为高温过程，第二次硼扩会影响轻扩曲线）。At present, the relatively mature boron SE scheme is mainly the secondary diffusion scheme; the first boron diffusion (light diffusion) - laser removal of local BSG (heavy diffusion area) - heavy diffusion (the light diffusion area is blocked by BSG, so as to achieve local heavy doping to complete the SE structure); the existing relatively mature technology is mainly the secondary diffusion scheme, 1. The two boron diffusions have a great impact on the production capacity, and multiple high-temperature diffusions affect the quality of the matrix, resulting in the loss of the final battery efficiency; 2. This scheme has very high requirements for laser (lossless film opening is required), which increases the equipment cost; 3. There is interference between the two boron diffusion processes (both are high-temperature processes, and the second boron diffusion will affect the light diffusion curve).
发明概述SUMMARY OF THE INVENTION 技术问题technical problem 问题的解决方案Solution to the problem 技术解决方案Technical Solutions
本发明的目的在于提供一种TOPCon电池的硼扩选择性发射极制备方法及电池制备工艺，以解决上述背景技术中提出的问题。The object of the present invention is to provide a method for preparing a boron-diffused selective emitter of a TOPCon battery and a battery preparation process to solve the problems raised in the above-mentioned background technology.
为实现上述目的，本发明提供如下技术方案：To achieve the above object, the present invention provides the following technical solutions:
一种TOPCon电池的硼扩选择性发射极制备方法，包括如下步骤：A method for preparing a boron-diffused selective emitter of a TOPCon cell comprises the following steps:
S1、硅片制绒样品正面或硼重扩正面成型一能够阻挡硼扩的掩膜层；S1, the front side of the silicon wafer texturing sample or the front side of the boron expansion is formed with a mask layer that can block the boron expansion;
S2、硅片重扩目标区域掩膜层改性或消融处理，形成不同硼扩性质的硼发射极硼扩区域；S2, modifying or ablating the mask layer of the target area of silicon wafer re-expansion to form a boron emitter boron expansion area with different boron expansion properties;
S3、硅片正面进行硼扩，不同性质的硼发射极硼扩区域得到不同扩散效果，形成选择性硼扩SE结构。S3. Boron diffusion is performed on the front side of the silicon wafer. Boron emitter diffusion areas with different properties obtain different diffusion effects, forming a selective boron diffusion SE structure.
本发明进一步提出了一种TOPCon电池的单次硼扩选择性发射极制备方法，包括如下步骤：The present invention further proposes a method for preparing a single boron diffusion selective emitter of a TOPCon cell, comprising the following steps:
Step1、采用涂覆、沉积、印刷或转印方式在制绒样品正面成型一可阻挡硼扩的掩膜层；Step 1, forming a mask layer capable of blocking boron diffusion on the front side of the texturing sample by coating, deposition, printing or transfer;
Step2、采用激光进行硅片重扩目标区域局部加热，使得硅片重扩目标区域的掩膜层在高温加热改性或消融后，不再阻挡硼扩形成重扩区，余下为轻扩区，形成不同硼扩性质的硼发射极硼扩区域；Step 2, using laser to locally heat the target area of silicon wafer re-expansion, so that after the mask layer of the target area of silicon wafer re-expansion is modified or ablated by high-temperature heating, it no longer blocks the boron expansion to form a re-expansion area, and the remaining is a light expansion area, forming a boron emitter boron expansion area with different boron expansion properties;
Step3、对上述硅片进行单次硼扩，不同硼扩性质的硼发射极硼扩区域在硼扩时，形成轻扩区和重扩区，形成硼扩选择性发射极SE结构。Step 3, perform a single boron expansion on the above silicon wafer. During the boron expansion, the boron emitter boron expansion regions with different boron expansion properties form light expansion areas and heavy expansion areas, forming a boron expansion selective emitter SE structure.
本发明进一步提出了一种基于上述硼扩选择性发射极制备方法并配合去绕镀反刻的电池制备工艺，包括如下步骤：The present invention further proposes a battery preparation process based on the above-mentioned boron diffusion selective emitter preparation method and combined with de-wrap plating and reverse etching, comprising the following steps:
步骤一：硅片制绒并正面硼扩重扩；Step 1: Silicon wafer texturing and front side boron expansion and re-expansion;
步骤二：硅片碱抛以及正面去除BSG；Step 2: Alkaline polishing of silicon wafer and removal of BSG on the front side;
步骤三：硅片正面成型能够受低功率激光改性的可阻挡硼扩的耐碱掩膜层；Step 3: Forming an alkali-resistant mask layer on the front side of the silicon wafer that can be modified by low-power laser and can block boron diffusion;
步骤四：低功率激光对硅片正面轻掺区的掩膜层改性，使得该区域掩膜层不再耐碱或直接消融、蒸发；Step 4: Use a low-power laser to modify the mask layer in the lightly doped area on the front side of the silicon wafer, so that the mask layer in this area is no longer alkali-resistant or is directly ablated or evaporated;
步骤五：硅片背面制备隧穿层以及非晶硅本征沉积，并进行高温磷扩；Step 5: Prepare a tunneling layer and amorphous silicon intrinsic deposition on the back of the silicon wafer, and perform high-temperature phosphorus diffusion;
步骤六：采用低温制绒工艺去除正面绕镀同时实现轻掺反刻，实现硼SE结构；随后硅片双面沉积三氧化二铝层以及氮化硅层；Step 6: Use low-temperature texturing process to remove the front side plating and realize light doping reverse etching to realize boron SE structure; then deposit aluminum oxide layer and silicon nitride layer on both sides of the silicon wafer;
步骤七：硅片表面处理，硅片背面印刷银浆电极、正面印刷银铝浆电极，然后烧结完成电池制备。Step 7: Surface treatment of silicon wafer: printing silver paste electrode on the back of silicon wafer and silver aluminum paste electrode on the front, and then sintering to complete battery preparation.
优选的，所述步骤一前预先制备硅片绒面，在KOH和H2O2混合溶液中去除硅片表面的损伤层，然后在KOH溶液中进行制绒，表面形成金字塔绒面，金字塔绒面大小控制1-5µm；所述步骤一中硅片正面硼扩重扩制备发射极，其方阻50-100 ohm/□；BSG厚度50-120 nm；所述步骤二硅片背面去BSG后进行碱抛，使硅片背面的反射率大于40%，碱抛后采用HF去除正面BSG。Preferably, the silicon wafer texture is prepared in advance before the step one, the damaged layer on the surface of the silicon wafer is removed in a mixed solution of KOH and H2O2, and then the texture is made in a KOH solution to form a pyramid texture on the surface, and the size of the pyramid texture is controlled to be 1-5µm; in the step one, the emitter is prepared by boron diffusion and re-diffusion on the front side of the silicon wafer, and its square resistance is 50-100 ohm/□; the BSG thickness is 50-120 nm; in the step two, the back side of the silicon wafer is alkaline polished after the BSG is removed, so that the reflectivity of the back side of the silicon wafer is greater than 40%, and HF is used to remove the BSG on the front side after the alkaline polishing.
优选的，所述步骤三中掩膜层为一类固态非金属化合物混合桨料，溶质包括非金属氧化物、硫化物、氮化物、磷化物和/或砷化物，溶剂包括水、苯乙烯、全氯乙烯、三氯乙烯、乙烯乙二醇醚和/或三乙醇胺。Preferably, the mask layer in step three is a solid non-metallic compound mixed slurry, the solute includes non-metallic oxides, sulfides, nitrides, phosphides and/or arsenides, and the solvent includes water, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and/or triethanolamine.
优选的，所述步骤三中耐碱掩膜层的成型方式为包括涂覆、沉积、印刷以及转印在内的任意一种；印刷方式采用400-500目，7-15μm线径全开口网版。Preferably, the alkali-resistant mask layer in step three is formed by any one of coating, deposition, printing and transfer; the printing method uses a 400-500 mesh, 7-15 μm line diameter full-opening screen.
优选的，所述步骤四中所述低功率激光改性处理是，采用300-500nm波长，20-40W功率大光斑50-200μm光斑尺寸的纳秒低功率激光，采用线扫方式对应栅线设计图形进行局部加热或开膜处理。Preferably, the low-power laser modification treatment in step 4 is to use a nanosecond low-power laser with a wavelength of 300-500nm, a power of 20-40W, a large spot size of 50-200μm, and a line scanning method to perform local heating or film opening treatment corresponding to the grid line design pattern.
优选的，所述步骤五中硅片背面在LPCVD中单面制备隧穿层1-2nm以及非晶硅本征沉积50-150nm，采用高温磷扩，扩散温度700-900℃，完成高温晶化与扩散。Preferably, in step five, a tunneling layer of 1-2 nm and an amorphous silicon intrinsic deposition of 50-150 nm are prepared on the back side of the silicon wafer in LPCVD, and high-temperature phosphorus diffusion is adopted with a diffusion temperature of 700-900° C. to complete high-temperature crystallization and diffusion.
优选的，所述步骤六中轻掺反刻的方阻130-300 ohm/□，硅片双面使用ALD沉积3-10nm厚度三氧化二铝，并使用PECVD制备75-80nm厚度的氮化硅，在硅片背面沉积70-100nm厚度的氮化硅。Preferably, in step six, the square resistance of the lightly doped reverse etch is 130-300 ohm/□, 3-10nm thick aluminum oxide is deposited on both sides of the silicon wafer using ALD, and 75-80nm thick silicon nitride is prepared using PECVD, and 70-100nm thick silicon nitride is deposited on the back of the silicon wafer.
优选的，所述步骤七中硅片表面钝化完成后，在硅片正面和背面进行金属化，用丝网印刷的方式依次在硅片背面印刷银浆电极、正面印刷银铝浆电极，然后烧结完成电池制备。Preferably, after the surface passivation of the silicon wafer is completed in step seven, metallization is performed on the front and back of the silicon wafer, and silver paste electrodes are printed on the back of the silicon wafer and silver aluminum paste electrodes are printed on the front in sequence by screen printing, and then sintering is performed to complete the battery preparation.
发明的有益效果Advantageous Effects of the Invention 有益效果Beneficial Effects
与现有技术相比，本发明的优点在于以下几个方面：Compared with the prior art, the advantages of the present invention are as follows:
本发明创造性地提出了一种基于一次激光的硼扩选择性发射极制备方法，有效提高产能，掩膜可通过涂覆、沉积、印刷或转印等方式制备；其中关键点在于可阻挡一定程度硼扩掩膜，高温加热后改性不再耐碱或不再阻挡硼扩。激光可采用纳秒低功率激光，成本低，便于控制，低功率激光后加热改性不再耐碱或直接消融；去绕镀采用低温制绒工艺，保护正面绒面的同时实现去Poly绕镀、轻掺反刻两个功能，良品率高。The present invention creatively proposes a method for preparing a selective emitter for boron diffusion based on a single laser, which effectively improves production capacity. The mask can be prepared by coating, deposition, printing or transfer, etc. The key point is that the mask can block a certain degree of boron diffusion, and after high-temperature heating, it is modified to no longer be alkali-resistant or no longer block boron diffusion. The laser can use a nanosecond low-power laser, which is low-cost and easy to control. After low-power laser heating, it is no longer alkali-resistant or directly ablated; the de-wrap plating adopts a low-temperature velvet process to protect the front velvet surface while realizing the two functions of de-poly wrap plating and light doping reverse engraving, with a high yield rate.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为一种TOPCon电池的硼扩选择性发射极制备方法的流程简图。FIG. 1 is a simplified flow chart of a method for preparing a boron-diffused selective emitter of a TOPCon cell.
图2为一种TOPCon电池的单次硼扩选择性发射极制备方法的流程简图。FIG. 2 is a simplified flow chart of a method for preparing a single boron diffusion selective emitter of a TOPCon cell.
图3为一种基于硼扩选择性发射极制备配合去绕镀反刻的电池制备工艺的流程简图。FIG3 is a simplified flow chart of a battery preparation process based on boron diffusion selective emitter preparation combined with de-wrap plating and reverse etching.
实施该发明的最佳实施例Best Mode for Carrying Out the Invention 本发明的最佳实施方式Best Mode for Carrying Out the Invention 具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
在本发明的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制；术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性；此外，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本发明中的具体含义。In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inside", "outside" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific position, be constructed and operated in a specific position, and therefore cannot be understood as limiting the present invention; the terms "first", "second", and "third" are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance; in addition, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be an indirect connection through an intermediate medium, or it can be a connection between the two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.
本发明在N型TOPCon电池上的具体实施案例如下：The specific implementation examples of the present invention on N-type TOPCon batteries are as follows:
实施例1：Embodiment 1:
请参阅图1-2；一种TOPCon电池的硼扩选择性发射极制备方法，包括如下步骤：Please refer to Figure 1-2; a method for preparing a boron-diffused selective emitter of a TOPCon cell includes the following steps:
Step1、采用涂覆、沉积、印刷或转印等方式在制绒样品正面沉积一层掩膜层（可阻挡一定程度硼扩）；在一些实施例中，掩膜层为一类固态非金属化合物混合桨料，能够阻挡硼扩，溶质包括非金属氧化物、硫化物、氮化物、磷化物和/或砷化物，溶剂包括水、苯乙烯、全氯乙烯、三氯乙烯、乙烯乙二醇醚和/或三乙醇胺；Step 1, deposit a mask layer (which can block a certain degree of boron diffusion) on the front of the texturing sample by coating, deposition, printing or transfer; in some embodiments, the mask layer is a solid non-metallic compound mixed slurry that can block boron diffusion, the solute includes non-metallic oxides, sulfides, nitrides, phosphides and/or arsenides, and the solvent includes water, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and/or triethanolamine;
Step2、采用激光进行局部加热，高温加热改性后掩膜不再阻挡硼扩；Step 2: Use laser for local heating. After high temperature heating and modification, the mask no longer blocks boron diffusion.
Step3、单次硼扩，未加热掩膜阻挡区域为轻扩区，加热改性后掩膜区为重扩区，形成硼扩选择性发射极SE结构。Step 3: Single boron expansion. The unheated mask blocking area is the light expansion area, and the heated and modified mask area is the heavy expansion area, forming a boron-expanded selective emitter SE structure.
实施例2：Embodiment 2:
请参阅图3；一种TOPCon电池的硼扩选择性发射极制备配合去绕镀反刻的电池制备工艺，包括如下步骤；选用电阻率范围0.8ohm.cm，少子寿命>2.5 ms的N型单晶硅片，厚度170µm，尺寸为210mm。Please refer to Figure 3; a TOPCon battery preparation process for boron-diffused selective emitter preparation combined with de-wrap plating and reverse etching, including the following steps; select N-type single crystal silicon wafers with a resistivity range of 0.8ohm.cm and a minority carrier lifetime of >2.5 ms, a thickness of 170µm, and a size of 210mm.
在KOH和H 2O 2混合溶液中去除硅片表面的损伤层，然后在KOH溶液中进行制绒，表面形成金字塔绒面，金字塔绒面大小控制3µm。 The damaged layer on the surface of the silicon wafer is removed in a mixed solution of KOH and H 2 O 2 , and then texturing is carried out in the KOH solution to form a pyramid velvet surface on the surface. The size of the pyramid velvet surface is controlled to be 3µm.
绒面完成后，在硅片正面采用B扩散重扩工艺（方阻70 ohm/□）制备发射极，BSG厚度80nm,硅片背面去BSG后进行碱抛，使硅片背面的反射率大于40%，碱抛后HF去除正面BSG；After the texture is completed, the emitter is prepared on the front side of the silicon wafer using the B diffusion re-expansion process (square resistance 70 ohm/□), the BSG thickness is 80nm, and the back side of the silicon wafer is alkaline polished after removing the BSG to make the reflectivity of the back side of the silicon wafer greater than 40%. After alkaline polishing, HF is used to remove the BSG on the front side;
采用转印方式在样品正面沉积一层掩膜层作为耐碱阻挡层；采用激光进行局部加热（轻掺区），高温加热改性后掩膜不再耐碱；在一些实施例中，掩膜层为一类固态非金属化合物混合桨料，能够阻挡硼扩，溶质包括非金属氧化物、硫化物、氮化物、磷化物和/或砷化物，溶剂包括水、苯乙烯、全氯乙烯、三氯乙烯、乙烯乙二醇醚和/或三乙醇胺；A mask layer is deposited on the front of the sample by transfer printing as an alkali-resistant barrier layer; laser is used for local heating (lightly doped area), and the mask is no longer alkali-resistant after high-temperature heating modification; in some embodiments, the mask layer is a type of solid non-metallic compound mixed slurry that can block boron diffusion, the solute includes non-metallic oxides, sulfides, nitrides, phosphides and/or arsenides, and the solvent includes water, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and/or triethanolamine;
背面在LPCVD中单面制备隧穿层2nm+非晶硅本征沉积100nm，采用高温磷扩扩散温度800℃完成高温晶化与扩散；On the back side, a 2nm tunneling layer + 100nm amorphous silicon intrinsic deposition is prepared on one side in LPCVD, and high-temperature crystallization and diffusion are completed using high-temperature phosphorus diffusion at a temperature of 800°C;
采用低温制绒工艺去除正面绕镀同时实现轻掺反刻（得到轻掺方阻200 ohm/□）后在硅片双面使用ALD沉积6nm厚度三氧化二铝，并使用PECVD制备75nm厚度的氮化硅；在硅片背面沉积70nm厚度的氮化硅，完成电池前驱体制备。A low-temperature texturing process is used to remove the front-side plating and achieve light-doped reverse etching (obtaining a light-doped square resistivity of 200 ohm/□). ALD is then used to deposit 6nm thick aluminum oxide on both sides of the silicon wafer, and PECVD is used to prepare 75nm thick silicon nitride; 70nm thick silicon nitride is deposited on the back of the silicon wafer to complete the preparation of the battery precursor.
表面钝化完成后在硅片正面和背面进行金属化，用丝网印刷的方式依次在硅片背面印刷银浆电极、正面印刷银铝浆电极，然后烧结完成电池制备。After surface passivation is completed, metallization is performed on the front and back of the silicon wafer. Silver paste electrodes are printed on the back of the silicon wafer and silver aluminum paste electrodes are printed on the front by screen printing, and then sintering is performed to complete the battery preparation.
上面对本专利的较佳实施方式作了详细说明，但是本专利并不限于上述实施方式，在本领域的普通技术人员所具备的知识范围内，还可以在不脱离本专利宗旨的前提下作出各种变化。The above describes in detail the preferred implementation of this patent, but this patent is not limited to the above implementation. Various changes can be made within the knowledge scope of ordinary technicians in this field without departing from the purpose of this patent.

Claims (10)

  1. 一种TOPCon电池的硼扩选择性发射极制备方法，其特征在于，包括如下步骤：A method for preparing a boron-diffused selective emitter of a TOPCon battery, characterized in that it comprises the following steps:
    S1、硅片制绒样品正面或硼重扩正面成型一能够阻挡硼扩的掩膜层；S1, the front side of the silicon wafer texturing sample or the front side of the boron expansion is formed with a mask layer that can block the boron expansion;
    S2、硅片重扩目标区域掩膜层改性或消融处理，形成不同硼扩性质的硼发射极硼扩区域；S2, modifying or ablating the mask layer of the target area of silicon wafer re-expansion to form a boron emitter boron expansion area with different boron expansion properties;
    S3、硅片正面进行硼扩，不同性质的硼发射极硼扩区域得到不同扩散效果，形成选择性硼扩SE结构。S3. Boron diffusion is performed on the front side of the silicon wafer. Boron emitter diffusion areas with different properties obtain different diffusion effects, forming a selective boron diffusion SE structure.
  2. 根据权利要求1所述的一种TOPCon电池的硼扩选择性发射极制备方法，其特征在于，包括如下步骤：The method for preparing a boron-diffused selective emitter of a TOPCon battery according to claim 1, characterized in that it comprises the following steps:
    Step1、采用涂覆、沉积、印刷或转印方式在制绒样品正面成型一可阻挡硼扩的掩膜层；Step 1, forming a mask layer capable of blocking boron diffusion on the front side of the texturing sample by coating, deposition, printing or transfer;
    Step2、采用激光进行硅片重扩目标区域局部加热，使得硅片重扩目标区域的掩膜层在高温加热改性或消融后，不再阻挡硼扩形成重扩区，余下为轻扩区，形成不同硼扩性质的硼发射极硼扩区域；Step 2, using laser to locally heat the target area of silicon wafer re-expansion, so that after the mask layer of the target area of silicon wafer re-expansion is modified or ablated by high-temperature heating, it no longer blocks the boron expansion to form a re-expansion area, and the remaining is a light expansion area, forming a boron emitter boron expansion area with different boron expansion properties;
    Step3、对上述硅片进行单次硼扩，不同硼扩性质的硼发射极硼扩区域在硼扩时，形成轻扩区和重扩区，形成硼扩选择性发射极SE结构。Step 3, perform a single boron expansion on the above silicon wafer. During the boron expansion, the boron emitter boron expansion regions with different boron expansion properties form light expansion areas and heavy expansion areas, forming a boron expansion selective emitter SE structure.
  3. 根据权利要求1所述的一种TOPCon电池的硼扩选择性发射极制备方法，其特征在于，所述掩膜层为一类固态非金属化合物混合桨料，溶质包括非金属氧化物、硫化物、氮化物、磷化物和/或砷化物，溶剂包括水、苯乙烯、全氯乙烯、三氯乙烯、乙烯乙二醇醚和/或三乙醇胺。According to claim 1, a method for preparing a boron-diffused selective emitter of a TOPCon battery is characterized in that the mask layer is a type of solid non-metallic compound mixed slurry, the solute includes non-metallic oxides, sulfides, nitrides, phosphides and/or arsenides, and the solvent includes water, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and/or triethanolamine.
  4. 一种基于权利要求1所述方法配合去绕镀反刻的电池制备工艺，其特征在于，A battery preparation process based on the method of claim 1 in combination with de-wrap plating and reverse etching, characterized in that:
    步骤一：硅片制绒并正面硼扩重扩；Step 1: Silicon wafer texturing and front side boron expansion and re-expansion;
    步骤二：硅片碱抛以及正面去除BSG；Step 2: Alkaline polishing of silicon wafer and removal of BSG on the front side;
    步骤三：硅片正面成型能够受激光改性的可阻挡硼扩的耐碱掩膜层；Step 3: Forming an alkali-resistant mask layer on the front side of the silicon wafer that can be modified by laser and can block boron diffusion;
    步骤四：激光对硅片正面轻掺区的掩膜层改性，使得该区域掩膜层不再耐碱或直接消融、蒸发；Step 4: The laser modifies the mask layer in the lightly doped area on the front side of the silicon wafer, so that the mask layer in this area is no longer alkali-resistant or is directly ablated or evaporated;
    步骤五：硅片背面制备隧穿层以及非晶硅本征沉积，并进行高温磷扩；Step 5: Prepare a tunneling layer and amorphous silicon intrinsic deposition on the back of the silicon wafer, and perform high-temperature phosphorus diffusion;
    步骤六：采用低温制绒工艺去除正面绕镀同时实现轻掺反刻，实现硼SE结构；随后硅片双面沉积三氧化二铝层以及氮化硅层；Step 6: Use low-temperature texturing process to remove the front side plating and realize light doping reverse etching to realize boron SE structure; then deposit aluminum oxide layer and silicon nitride layer on both sides of the silicon wafer;
    步骤七：硅片表面处理，硅片背面印刷银浆电极、正面印刷银铝浆电极，然后烧结完成电池制备。Step 7: Surface treatment of silicon wafer: printing silver paste electrode on the back of silicon wafer and silver aluminum paste electrode on the front, and then sintering to complete battery preparation.
  5. 根据权利要求4所述的电池制备工艺，其特征在于，所述步骤一前预先制备硅片绒面，在KOH和H 2O 2混合溶液中去除硅片表面的损伤层，然后在KOH溶液中进行制绒，表面形成金字塔绒面，金字塔绒面大小控制1-5µm；所述步骤一中硅片正面硼扩重扩制备发射极，其方阻50-100 ohm/□；BSG厚度50-120 nm；所述步骤二硅片背面去BSG后进行碱抛，使硅片背面的反射率大于40%，碱抛后采用HF去除正面BSG。 The battery preparation process according to claim 4 is characterized in that, before the step 1, a silicon wafer texture is prepared in advance, the damaged layer on the surface of the silicon wafer is removed in a mixed solution of KOH and H2O2 , and then the texture is made in the KOH solution to form a pyramid texture on the surface, and the size of the pyramid texture is controlled to be 1-5µm; in the step 1, the emitter is prepared by boron expansion and re-expansion on the front side of the silicon wafer, and its square resistance is 50-100 ohm/□; the BSG thickness is 50-120 nm; in the step 2, the back side of the silicon wafer is alkaline polished after removing the BSG, so that the reflectivity of the back side of the silicon wafer is greater than 40%, and HF is used to remove the front BSG after the alkaline polishing.
  6. 根据权利要求4所述的电池制备工艺，其特征在于，所述步骤三中耐碱掩膜层的成型方式为包括涂覆、沉积、印刷以及转印在内的任意一种；印刷方式采用400-500目，7-15μm线径全开口网版。The battery preparation process according to claim 4 is characterized in that the forming method of the alkali-resistant mask layer in step three is any one of coating, deposition, printing and transfer; the printing method adopts a 400-500 mesh, 7-15 μm line diameter full-opening screen.
  7. 根据权利要求4所述的电池制备工艺，其特征在于，所述步骤四中所述激光改性处理是，采用300-500nm波长，20-40W功率大光斑50-200μm光斑尺寸的纳秒低功率激光，采用线扫方式对应栅线设计图形进行局部加热或开膜处理。The battery preparation process according to claim 4 is characterized in that the laser modification treatment in step 4 is to use a nanosecond low-power laser with a wavelength of 300-500nm, a power of 20-40W, a large spot size of 50-200μm, and a line scanning method to perform local heating or film opening treatment corresponding to the grid line design pattern.
  8. 根据权利要求4所述的电池制备工艺，其特征在于，所述步骤五中硅片背面在LPCVD中单面制备隧穿层1-2nm以及非晶硅本征沉积50-150nm，采用高温磷扩，扩散温度700-900℃，完成高温晶化与扩散。The battery preparation process according to claim 4 is characterized in that in the step 5, a tunneling layer of 1-2 nm and an amorphous silicon intrinsic deposition of 50-150 nm are prepared on the back side of the silicon wafer in LPCVD, and high-temperature phosphorus diffusion is adopted with a diffusion temperature of 700-900°C to complete high-temperature crystallization and diffusion.
  9. 根据权利要求4所述的电池制备工艺，其特征在于，所述步骤六中轻掺反刻的方阻130-300 ohm/□，硅片双面使用ALD沉积3-10nm厚度三氧化二铝，并使用PECVD制备75-80nm厚度的氮化硅，在硅片背面沉积70-100nm厚度的氮化硅。The battery preparation process according to claim 4 is characterized in that the square resistance of the lightly doped reverse etched in step 6 is 130-300 ohm/□, aluminum oxide with a thickness of 3-10nm is deposited on both sides of the silicon wafer using ALD, and silicon nitride with a thickness of 75-80nm is prepared using PECVD, and silicon nitride with a thickness of 70-100nm is deposited on the back of the silicon wafer.
  10. 根据权利要求4所述的电池制备工艺，其特征在于，所述步骤七中硅片表面钝化完成后，在硅片正面和背面进行金属化，用丝网印刷的方式依次在硅片背面印刷银浆电极、正面印刷银铝浆电极，然后烧结完成电池制备。The battery preparation process according to claim 4 is characterized in that after the surface passivation of the silicon wafer is completed in the step 7, metallization is performed on the front and back of the silicon wafer, and a silver paste electrode is printed on the back of the silicon wafer and a silver-aluminum paste electrode is printed on the front in sequence by screen printing, and then sintering is performed to complete the battery preparation.
PCT/CN2023/131449 2022-12-05 2023-11-14 Boron-diffusion selective emitter preparation method for topcon battery, and battery preparation process WO2024120129A1 (en)

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