WO2022001294A1 - Method for preparing laser se battery - Google Patents

Method for preparing laser se battery Download PDF

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WO2022001294A1
WO2022001294A1 PCT/CN2021/087702 CN2021087702W WO2022001294A1 WO 2022001294 A1 WO2022001294 A1 WO 2022001294A1 CN 2021087702 W CN2021087702 W CN 2021087702W WO 2022001294 A1 WO2022001294 A1 WO 2022001294A1
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laser
silicon wafer
psg
phosphorus source
preparing
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PCT/CN2021/087702
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French (fr)
Chinese (zh)
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任常瑞
张佳舟
赵潇祺
王敏
符黎明
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常州时创能源股份有限公司
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Publication of WO2022001294A1 publication Critical patent/WO2022001294A1/en

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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
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table
    • H01L31/0288—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table characterised by the doping material
    • 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1868—Passivation
    • 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 present invention relates to a preparation method of a laser SE battery.
  • the production of PERC technology has matured.
  • SE technology is the first choice for photovoltaic enterprises.
  • the role of the lightly doped region is mainly to form a built-in electric field to separate the electron-hole pair, while the heavily doped region has to play the role of contacting the metal, and the two have requirements for the doping curve. different.
  • the application of laser doping technology further optimizes the metal contact part, but the laser doping energy is limited. While obtaining better metal contact, the laser damage caused by the higher laser energy increases the number of defects in the heavily doped region and affects the electrical properties. . In order to balance the gain and loss of electrical properties caused by metal contact and laser damage, the doping of the lightly doped region cannot be further reduced, which restricts the space for electrical properties to improve.
  • the preparation process of the selective emitter is further optimized to further reduce the doping energy of the lightly doped region, and it is particularly important to directional control the diffusion distribution of the lightly doped region.
  • the purpose of the present invention is to provide a preparation method of a laser SE battery, which can make more active P atoms react to generate PSG in the near-surface region of the lightly doped region, thicken the PSG layer in the lightly doped region, and make the lightly doped region thicker.
  • the number of active phosphorus atoms is reduced, and the doping concentration in the near-surface region of the lightly doped region is reduced, while the surface concentration of the heavily doped region is basically unchanged, so as to achieve the purpose of directional regulation of the lightly doped region, thereby reducing the surface recombination of the cell and increasing the open voltage. Better electrical performance.
  • the present invention provides a preparation method of a laser SE battery, which includes laser doping and PSG removal, and also includes liquid-phase deposition of a phosphorus source and thermal oxidation. Thermal oxidation, and thermal oxidation is performed before de-PSG.
  • spin coating, spray coating or roller coating is used for the liquid phase deposition of the phosphorus source.
  • the phosphorus source is phosphoric acid, P 2 O 5 or polyphosphoric acid.
  • the concentration of the phosphorus source is 0.05-2.5 mol/L.
  • the deposition thickness of the phosphorus source is 0.1-20 ⁇ m.
  • the thermal oxidation is carried out in a chain furnace or a tube furnace.
  • the thermal oxidation atmosphere is oxygen, nitrogen-oxygen mixture or water-oxygen mixture.
  • the temperature of the thermal oxidation is 650-900°C.
  • the thermal oxidation time is 30s ⁇ 1h.
  • the specific steps of the above-mentioned preparation method of laser SE battery include:
  • a preparation method of a laser SE battery which can make the near-surface region of the lightly doped region have more active P atoms to react to generate PSG, so that the PSG layer of the lightly doped region can be thickened,
  • the number of active phosphorus atoms in the lightly doped region is reduced, and the doping concentration in the near-surface region of the lightly doped region is reduced, while the surface concentration of the heavily doped region is basically unchanged, so as to achieve the purpose of directional regulation of the lightly doped region, thereby reducing the recombination of the cell surface.
  • the open voltage is improved, and the electrical performance is better.
  • a lightly doped region and a heavily doped region will be formed on the front side of the silicon wafer.
  • the PSG layer in the heavily doped region is destroyed by the laser, while the PSG layer in the lightly doped region remains.
  • the present invention adds liquid phase deposition phosphorus source and thermal oxidation between laser doping and PSG removal. Due to the existence of the PSG layer in the lightly doped region, during the thermal oxidation process, the liquid phase deposited phosphorus source diffuses, and the PSG layer in the lightly doped region will Playing a blocking role, a large amount of free P will accumulate at the Si/SiO 2 interface.
  • the free P reacts to generate a large amount of P 2 O 5 , and further reacts with the Si at the interface to generate PSG, so that the light doped
  • the PSG layer in the lightly doped region is thickened, the number of active P atoms in the lightly doped region decreases, and the doping concentration near the surface region decreases in the lightly doped region; while in the heavily doped region, because the PSG layer is destroyed by the laser, the reaction and the diffusion of the lightly doped region occur. The process is not consistent, so there is no obvious doping change trend.
  • the invention provides a preparation method of a laser SE battery, comprising the following steps:
  • Thermal oxidation is carried out on the silicon wafer after liquid deposition to redistribute the light and heavy doped areas; thermal oxidation is carried out in a chain furnace or a tube furnace, and the atmosphere is oxygen, nitrogen-oxygen mixture or water-oxygen mixture, and the temperature is 650 ⁇ 900°C, the time is 30s ⁇ 1h;
  • a preparation method of a laser SE battery comprising the following steps:
  • Thermal oxidation is carried out on the silicon wafer after liquid deposition to redistribute the light and heavy doped regions; thermal oxidation is carried out in a chain furnace or a tube furnace, the atmosphere is oxygen, the temperature is 650 °C, and the time is 100s;
  • step 4) and step 5) are omitted, and other process steps and process conditions remain unchanged.
  • a preparation method of a laser SE battery comprising the following steps:
  • Liquid-phase deposition of a phosphorus source is performed on the laser-doped silicon wafer, and the deposited phosphorus source covers the front side of the silicon wafer; the liquid-phase deposition of the phosphorus source is sprayed; the phosphorus source is an organic solution of P 2 O 5 ; the concentration of the phosphorus source is 2.5mol/L; the deposition thickness of phosphorus source is 5 ⁇ m;
  • Thermal oxidation is carried out on the silicon wafer after liquid deposition to redistribute the light and heavy doping areas; thermal oxidation is carried out in a chain furnace or a tube furnace, the atmosphere is a nitrogen-oxygen mixture, the temperature is 680 °C, and the time is 50s;
  • step 4) and step 5) are omitted, and other process steps and process conditions remain unchanged.
  • a preparation method of a laser SE battery comprising the following steps:
  • Liquid-phase deposition of a phosphorus source is performed on the laser-doped silicon wafer, and the deposited phosphorus source covers the front of the silicon wafer; the liquid-phase deposition of the phosphorus source is carried out by roller coating; the phosphorus source is an organic solution of polyphosphoric acid; the concentration of the phosphorus source is 2.5mol/L; the deposition thickness of phosphorus source is 10 ⁇ m;
  • Thermal oxidation is carried out on the silicon wafer after liquid deposition to redistribute the light and heavy doped areas; thermal oxidation is carried out in a chain furnace or a tube furnace, the atmosphere is a mixture of water and oxygen, the temperature is 680 °C, and the time is 50s;
  • step 4) and step 5) are omitted, and other process steps and process conditions remain unchanged.
  • test equipment used for the test of the doping concentration is Wafer Profiler CVP21
  • test standard is GB/T 14146-2009 "Determination of Carrier Concentration in Silicon Epitaxial Layer - Mercury Probe Capacitance-Voltage Method”
  • test equipment used is HALM tester
  • test standard is JB/T 9478.3-2013 "Photoelectric Cell Measurement Methods Part 3 Photoelectric Conversion Efficiency”.
  • the phosphorus source concentration in the near-surface region of the lightly doped region is significantly reduced, the open voltage is increased, and the electrical performance is improved.
  • the concentration in the near-surface region of the lightly doped region is significantly reduced, so that the final open voltage is significantly improved, and the electrical performance is improved.

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  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
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Abstract

Disclosed is a method for preparing a laser SE battery, the method comprising laser doping and the removal of PSG, and further comprising the liquid phase deposition of a phosphorus source and the thermal oxidation thereof, wherein after laser doping, the phosphorus source is first subjected to liquid phase deposition and is then thermally oxidized, which is implemented prior to the removal of PSG. In the present invention, more active P atoms can be reacted in a near-surface region of a lightly doped region to generate PSG, so as to thicken a PSG layer in the lightly doped region, reduce the number of active phosphorus atoms in the lightly doped region and reduce the doping concentration in the near-surface region of the lightly doped region, with the surface concentration of a heavily doped region being basically unchanged, so as to achieve the aim of the directional regulation of the lightly doped region, such that a battery piece has reduced surface compounding, an increased open voltage, and better electrical performance.

Description

激光SE电池的制备方法Preparation method of laser SE battery 技术领域technical field
本发明涉及激光SE电池的制备方法。The present invention relates to a preparation method of a laser SE battery.
背景技术Background technique
太阳能光伏发电，由于其清洁、安全、便利及高效等特点，已成为全世界普遍关注和重点发展的新兴产业。近年来晶硅太阳能电池片生产迅速发展，技术不断进步。Solar photovoltaic power generation, because of its cleanliness, safety, convenience and high efficiency, has become an emerging industry that is widely concerned and developed around the world. In recent years, the production of crystalline silicon solar cells has developed rapidly, and the technology has continued to improve.
当前太阳能技术中，PERC技术生产已经成熟化，为了提升转化率，选择SE技术是各光伏企业的首选。在PERC+SE的技术路线中，轻掺区的作用主要是形成内建电场使电子-空穴对分开，而重掺区则要起到与金属接触的作用，二者对掺杂曲线的要求不同。激光掺杂技术的应用使金属接触部分进一步优化，但激光掺杂能量有限，更高的激光能量在获得更好金属接触的同时，造成的激光损伤使重掺区缺陷数目增加，电性能受到影响。为平衡金属接触与激光损伤带来的电性能增益与损失，轻掺区的掺杂无法进一步降低，制约了电性能上升的空间。In the current solar energy technology, the production of PERC technology has matured. In order to improve the conversion rate, the choice of SE technology is the first choice for photovoltaic enterprises. In the technical route of PERC+SE, the role of the lightly doped region is mainly to form a built-in electric field to separate the electron-hole pair, while the heavily doped region has to play the role of contacting the metal, and the two have requirements for the doping curve. different. The application of laser doping technology further optimizes the metal contact part, but the laser doping energy is limited. While obtaining better metal contact, the laser damage caused by the higher laser energy increases the number of defects in the heavily doped region and affects the electrical properties. . In order to balance the gain and loss of electrical properties caused by metal contact and laser damage, the doping of the lightly doped region cannot be further reduced, which restricts the space for electrical properties to improve.
在此基础上，进一步优化选择性发射极的制备过程，使轻掺区的掺杂能进一步降低，对轻掺区的扩散分布进行定向调控显得尤为重要。On this basis, the preparation process of the selective emitter is further optimized to further reduce the doping energy of the lightly doped region, and it is particularly important to directional control the diffusion distribution of the lightly doped region.
技术解决方案technical solutions
本发明的目的在于提供一种激光SE电池的制备方法，其可以使轻掺区的近表面区有更多的活性P原子反应生成PSG，使轻掺区的PSG层增厚，使轻掺区的活性磷原子数目减少，降低轻掺区近表面区的掺杂浓度，而重掺区表面浓度基本不变，达到定向调控轻掺区的目的，从而使电池片表面复合减少，开压提高，电性能更优。The purpose of the present invention is to provide a preparation method of a laser SE battery, which can make more active P atoms react to generate PSG in the near-surface region of the lightly doped region, thicken the PSG layer in the lightly doped region, and make the lightly doped region thicker. The number of active phosphorus atoms is reduced, and the doping concentration in the near-surface region of the lightly doped region is reduced, while the surface concentration of the heavily doped region is basically unchanged, so as to achieve the purpose of directional regulation of the lightly doped region, thereby reducing the surface recombination of the cell and increasing the open voltage. Better electrical performance.
为实现上述目的，本发明提供一种激光SE电池的制备方法，包括激光掺杂和去PSG，还包括液相沉积磷源和热氧化，在激光掺杂之后，先液相沉积磷源，再热氧化，且热氧化在去PSG之前实施。In order to achieve the above purpose, the present invention provides a preparation method of a laser SE battery, which includes laser doping and PSG removal, and also includes liquid-phase deposition of a phosphorus source and thermal oxidation. Thermal oxidation, and thermal oxidation is performed before de-PSG.
优选的，所述液相沉积磷源采用旋涂、喷涂或滚涂。Preferably, spin coating, spray coating or roller coating is used for the liquid phase deposition of the phosphorus source.
优选的，所述磷源为磷酸、P 2O 5或多聚磷酸。 Preferably, the phosphorus source is phosphoric acid, P 2 O 5 or polyphosphoric acid.
优选的，所述磷源的浓度为0.05～2.5mol/L。Preferably, the concentration of the phosphorus source is 0.05-2.5 mol/L.
优选的，所述磷源的沉积厚度为0.1～20μm。Preferably, the deposition thickness of the phosphorus source is 0.1-20 μm.
优选的，所述热氧化在链式炉或管式炉中实施。Preferably, the thermal oxidation is carried out in a chain furnace or a tube furnace.
优选的，所述热氧化的氛围为氧气、氮氧混合气或水氧混合气。Preferably, the thermal oxidation atmosphere is oxygen, nitrogen-oxygen mixture or water-oxygen mixture.
优选的，所述热氧化的温度为650～900℃。Preferably, the temperature of the thermal oxidation is 650-900°C.
优选的，所述热氧化的时间为30s～1h。Preferably, the thermal oxidation time is 30s˜1h.
优选的，上述激光SE电池的制备方法，其具体步骤包括：Preferably, the specific steps of the above-mentioned preparation method of laser SE battery include:
1）硅片正面去除损伤层再制绒；1) Remove the damaged layer on the front of the silicon wafer and retexture;
2）对完成制绒的硅片进行管式扩散；2) Tubular diffusion on the finished silicon wafer;
3）对完成管式扩散的硅片进行激光掺杂，在硅片正面形成重掺区；3) Perform laser doping on the silicon wafer that has completed the tubular diffusion, and form a heavily doped region on the front side of the silicon wafer;
4）对完成激光掺杂的硅片进行液相沉积磷源，沉积的磷源覆盖硅片正面；4) Liquid-phase deposition of a phosphorus source on the laser-doped silicon wafer, and the deposited phosphorus source covers the front of the silicon wafer;
5）对完成液相沉积的硅片进行热氧化，使轻重掺区重新分布；5) Thermal oxidation is performed on the silicon wafer after liquid deposition to redistribute the light and heavy doped regions;
6）对完成热氧化的硅片进行去PSG和去边结；6) Remove PSG and edge junction on the thermally oxidized silicon wafer;
7）对完成去PSG和去边结的硅片进行镀膜，在硅片正面沉积一层起减反射和钝化作用的氮化硅膜；7) Coating the silicon wafer with PSG removal and edge junction removal, and depositing a silicon nitride film for anti-reflection and passivation on the front of the silicon wafer;
8）对完成镀膜的硅片进行丝印和烧结，印刷背电极、背电场和正电极，再进行烧结，电极金属化，得到具有选择性发射极的电池片。8) Screen printing and sintering the coated silicon wafer, printing the back electrode, the back electric field and the positive electrode, and then sintering and metallizing the electrode to obtain a cell with a selective emitter.
有益效果beneficial effect
本发明的优点和有益效果在于：提供一种激光SE电池的制备方法，其可以使轻掺区的近表面区有更多的活性P原子反应生成PSG，使轻掺区的PSG层增厚，使轻掺区的活性磷原子数目减少，降低轻掺区近表面区的掺杂浓度，而重掺区表面浓度基本不变，达到定向调控轻掺区的目的，从而使电池片表面复合减少，开压提高，电性能更优。The advantages and beneficial effects of the present invention are as follows: a preparation method of a laser SE battery is provided, which can make the near-surface region of the lightly doped region have more active P atoms to react to generate PSG, so that the PSG layer of the lightly doped region can be thickened, The number of active phosphorus atoms in the lightly doped region is reduced, and the doping concentration in the near-surface region of the lightly doped region is reduced, while the surface concentration of the heavily doped region is basically unchanged, so as to achieve the purpose of directional regulation of the lightly doped region, thereby reducing the recombination of the cell surface. The open voltage is improved, and the electrical performance is better.
激光掺杂完成后，会在硅片正面形成轻掺区和重掺区，重掺区的PSG层被激光破坏，而轻掺区的PSG层保留。本发明在激光掺杂和去PSG之间增加液相沉积磷源和热氧化，由于轻掺区PSG层的存在，热氧化过程中，液相沉积的磷源扩散，轻掺区的PSG层会起到阻挡作用，会有大量自由P堆积在Si/SiO 2界面，在氧气的作用下，自由P反应生成大量的P 2O 5，并进一步与界面处的Si反应生成PSG，从而使轻掺区的PSG层增厚，轻掺区的活性P原子数目减少，轻掺区出现近表面区掺杂浓度下降的现象；而重掺区由于PSG层被激光破坏，发生的反应与轻掺区扩散过程不一致，因而不会出现明显掺杂变化趋势。 After the laser doping is completed, a lightly doped region and a heavily doped region will be formed on the front side of the silicon wafer. The PSG layer in the heavily doped region is destroyed by the laser, while the PSG layer in the lightly doped region remains. The present invention adds liquid phase deposition phosphorus source and thermal oxidation between laser doping and PSG removal. Due to the existence of the PSG layer in the lightly doped region, during the thermal oxidation process, the liquid phase deposited phosphorus source diffuses, and the PSG layer in the lightly doped region will Playing a blocking role, a large amount of free P will accumulate at the Si/SiO 2 interface. Under the action of oxygen, the free P reacts to generate a large amount of P 2 O 5 , and further reacts with the Si at the interface to generate PSG, so that the light doped The PSG layer in the lightly doped region is thickened, the number of active P atoms in the lightly doped region decreases, and the doping concentration near the surface region decreases in the lightly doped region; while in the heavily doped region, because the PSG layer is destroyed by the laser, the reaction and the diffusion of the lightly doped region occur. The process is not consistent, so there is no obvious doping change trend.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
下面结合实施例，对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。The specific embodiments of the present invention will be further described below with reference to the examples. The following examples are only used to illustrate the technical solutions of the present invention more clearly, and cannot be used to limit the protection scope of the present invention.
本发明提供一种激光SE电池的制备方法，包括如下步骤：The invention provides a preparation method of a laser SE battery, comprising the following steps:
1）硅片正面去除损伤层再制绒；1) Remove the damaged layer on the front of the silicon wafer and retexture;
2）对完成制绒的硅片进行管式扩散；2) Tubular diffusion on the finished silicon wafer;
3）对完成管式扩散的硅片进行激光掺杂，在硅片正面形成重掺区；3) Perform laser doping on the silicon wafer that has completed the tubular diffusion, and form a heavily doped region on the front side of the silicon wafer;
4）对完成激光掺杂的硅片进行液相沉积磷源，沉积的磷源覆盖硅片正面；液相沉积磷源采用旋涂、喷涂或滚涂；磷源为磷酸、P 2O 5或多聚磷酸的有机溶液；磷源的浓度为0.05～2.5mol/L；磷源的沉积厚度为0.1～20μm； 4) Liquid-phase deposition of the phosphorous source on the laser-doped silicon wafer, and the deposited phosphorous source covers the front of the silicon wafer; the liquid-phase deposited phosphorous source is applied by spin coating, spraying or roller coating; the phosphorous source is phosphoric acid, P 2 O 5 or The organic solution of polyphosphoric acid; the concentration of phosphorus source is 0.05～2.5mol/L; the deposition thickness of phosphorus source is 0.1～20μm;
5）对完成液相沉积的硅片进行热氧化，使轻重掺区重新分布；热氧化在链式炉或管式炉中实施，氛围为氧气、氮氧混合气或水氧混合气，温度为650～900℃，时间为30s～1h；5) Thermal oxidation is carried out on the silicon wafer after liquid deposition to redistribute the light and heavy doped areas; thermal oxidation is carried out in a chain furnace or a tube furnace, and the atmosphere is oxygen, nitrogen-oxygen mixture or water-oxygen mixture, and the temperature is 650～900℃, the time is 30s～1h;
6）对完成热氧化的硅片进行去PSG和去边结；6) Remove PSG and edge junction on the thermally oxidized silicon wafer;
7）对完成去PSG和去边结的硅片进行镀膜，在硅片正面沉积一层起减反射和钝化作用的氮化硅膜；7) Coating the silicon wafer with PSG removal and edge junction removal, and depositing a silicon nitride film for anti-reflection and passivation on the front of the silicon wafer;
8）对完成镀膜的硅片进行丝印和烧结，印刷背电极、背电场和正电极，再进行烧结，电极金属化，得到具有选择性发射极的电池片。8) Screen printing and sintering the coated silicon wafer, printing the back electrode, the back electric field and the positive electrode, and then sintering and metallizing the electrode to obtain a cell with a selective emitter.
本发明的具体实施例如下：Specific embodiments of the present invention are as follows:
实施例1Example 1
一种激光SE电池的制备方法，包括如下步骤：A preparation method of a laser SE battery, comprising the following steps:
1）硅片正面去除损伤层再制绒；1) Remove the damaged layer on the front of the silicon wafer and retexture;
2）对完成制绒的硅片进行管式扩散，以氮气为携磷气体，三氯氧磷为磷源，扩散温度为750℃，扩散时间为20min；2) Tubular diffusion is performed on the silicon wafers that have finished texturing, using nitrogen as the phosphorus-carrying gas, phosphorus oxychloride as the phosphorus source, the diffusion temperature is 750 °C, and the diffusion time is 20 minutes;
3）对完成管式扩散的硅片进行激光掺杂，在硅片正面形成重掺区；激光功率为28W，频率为246kHz；3) Doping the silicon wafer with tube diffusion by laser to form a heavily doped area on the front of the silicon wafer; the laser power is 28W and the frequency is 246kHz;
4）对完成激光掺杂的硅片进行液相沉积磷源，沉积的磷源覆盖硅片正面；液相沉积磷源采用旋涂；磷源为磷酸的有机溶液；磷源的浓度为1.0mol/L；磷源的沉积厚度为5μm；4) Liquid-phase deposition of the phosphorous source on the laser-doped silicon wafer, and the deposited phosphorous source covers the front of the silicon wafer; the liquid-phase deposition of the phosphorous source adopts spin coating; the phosphorous source is an organic solution of phosphoric acid; the concentration of the phosphorous source is 1.0 mol /L; the deposition thickness of the phosphorus source is 5 μm;
5）对完成液相沉积的硅片进行热氧化，使轻重掺区重新分布；热氧化在链式炉或管式炉中实施，氛围为氧气，温度为650℃，时间为100s；5) Thermal oxidation is carried out on the silicon wafer after liquid deposition to redistribute the light and heavy doped regions; thermal oxidation is carried out in a chain furnace or a tube furnace, the atmosphere is oxygen, the temperature is 650 °C, and the time is 100s;
6）对完成热氧化的硅片进行去PSG和去边结，在0.2wt%浓度HF中反应300s去除PSG和边结；6) Remove PSG and edge junctions on the thermally oxidized silicon wafer, and react in 0.2wt% HF for 300s to remove PSG and edge junctions;
7）对完成去PSG和去边结的硅片进行镀膜，在硅片正面沉积一层起减反射和钝化作用的氮化硅膜；7) Coating the silicon wafer with PSG removal and edge junction removal, and depositing a silicon nitride film for anti-reflection and passivation on the front of the silicon wafer;
8）对完成镀膜的硅片进行丝印和烧结，印刷背电极、背电场和正电极，再进行烧结，电极金属化，得到具有选择性发射极的电池片。8) Screen printing and sintering the coated silicon wafer, printing the back electrode, the back electric field and the positive electrode, and then sintering and metallizing the electrode to obtain a cell with a selective emitter.
对比例1Comparative Example 1
在实施例1的基础上，区别仅在于省去步骤4）和步骤5），其他工艺步骤和工艺条件不变。On the basis of Example 1, the difference is only that step 4) and step 5) are omitted, and other process steps and process conditions remain unchanged.
实施例1所得电池片与对比例1所得电池片的测试对比如表1所示：The test comparison ratio of the battery sheet obtained in Example 1 and the battery sheet obtained in Comparative Example 1 is shown in Table 1:
表1 实施例1所得电池片与对比例1所得电池片的测试对比Table 1 Test comparison between the cell obtained in Example 1 and the cell obtained in Comparative Example 1
Figure dest_path_image001
Figure dest_path_image001
实施例2Example 2
一种激光SE电池的制备方法，包括如下步骤：A preparation method of a laser SE battery, comprising the following steps:
1）硅片正面去除损伤层再制绒；1) Remove the damaged layer on the front of the silicon wafer and retexture;
2）对完成制绒的硅片进行管式扩散，以氮气为携磷气体，三氯氧磷为磷源，扩散温度为780℃，扩散时间为20min；2) Tubular diffusion is performed on the silicon wafers that have finished texturing, using nitrogen as the phosphorus-carrying gas, phosphorus oxychloride as the phosphorus source, the diffusion temperature is 780 °C, and the diffusion time is 20 minutes;
3）对完成管式扩散的硅片进行激光掺杂，在硅片正面形成重掺区；激光功率为30W，频率为240kHz；3) Doping the silicon wafer with tube diffusion by laser to form a heavily doped area on the front of the silicon wafer; the laser power is 30W and the frequency is 240kHz;
4）对完成激光掺杂的硅片进行液相沉积磷源，沉积的磷源覆盖硅片正面；液相沉积磷源采用喷涂；磷源为P 2O 5的有机溶液；磷源的浓度为2.5mol/L；磷源的沉积厚度为5μm； 4) Liquid-phase deposition of a phosphorus source is performed on the laser-doped silicon wafer, and the deposited phosphorus source covers the front side of the silicon wafer; the liquid-phase deposition of the phosphorus source is sprayed; the phosphorus source is an organic solution of P 2 O 5 ; the concentration of the phosphorus source is 2.5mol/L; the deposition thickness of phosphorus source is 5μm;
5）对完成液相沉积的硅片进行热氧化，使轻重掺区重新分布；热氧化在链式炉或管式炉中实施，氛围为氮氧混合气，温度为680℃，时间为50s；5) Thermal oxidation is carried out on the silicon wafer after liquid deposition to redistribute the light and heavy doping areas; thermal oxidation is carried out in a chain furnace or a tube furnace, the atmosphere is a nitrogen-oxygen mixture, the temperature is 680 °C, and the time is 50s;
6）对完成热氧化的硅片进行去PSG和去边结；在0.2wt%浓度HF中反应300s去除PSG和边结；6) Remove PSG and edge junctions on the thermally oxidized silicon wafer; remove PSG and edge junctions by reacting in 0.2wt% HF for 300s;
7）对完成去PSG和去边结的硅片进行镀膜，在硅片正面沉积一层起减反射和钝化作用的氮化硅膜；7) Coating the silicon wafer with PSG removal and edge junction removal, and depositing a silicon nitride film for anti-reflection and passivation on the front of the silicon wafer;
8）对完成镀膜的硅片进行丝印和烧结，印刷背电极、背电场和正电极，再进行烧结，电极金属化，得到具有选择性发射极的电池片。8) Screen printing and sintering the coated silicon wafer, printing the back electrode, the back electric field and the positive electrode, and then sintering and metallizing the electrode to obtain a cell with a selective emitter.
对比例2Comparative Example 2
在实施例2的基础上，区别仅在于省去步骤4）和步骤5），其他工艺步骤和工艺条件不变。On the basis of Example 2, the difference is only that step 4) and step 5) are omitted, and other process steps and process conditions remain unchanged.
实施例2所得电池片与对比例2所得电池片的测试对比如表2所示：The test comparison of the obtained cell of Example 2 and the cell of Comparative Example 2 is shown in Table 2:
表2 实施例2所得电池片与对比例2所得电池片的测试对比Table 2 Test comparison of the cell obtained in Example 2 and the cell obtained in Comparative Example 2
Figure 895947dest_path_image002
Figure 895947dest_path_image002
实施例3Example 3
一种激光SE电池的制备方法，包括如下步骤：A preparation method of a laser SE battery, comprising the following steps:
1）硅片正面去除损伤层再制绒；1) Remove the damaged layer on the front of the silicon wafer and retexture;
2）对完成制绒的硅片进行管式扩散,以氮气为携磷气体，三氯氧磷为磷源，扩散温度为800℃，扩散时间为20min；2) Tubular diffusion is performed on the silicon wafers that have finished texturing, using nitrogen as the phosphorus-carrying gas, phosphorus oxychloride as the phosphorus source, the diffusion temperature is 800 ℃, and the diffusion time is 20 minutes;
3）对完成管式扩散的硅片进行激光掺杂，在硅片正面形成重掺区；激光功率为30W，频率为240kHz；3) Doping the silicon wafer with tube diffusion by laser to form a heavily doped area on the front of the silicon wafer; the laser power is 30W and the frequency is 240kHz;
4）对完成激光掺杂的硅片进行液相沉积磷源，沉积的磷源覆盖硅片正面；液相沉积磷源采用滚涂；磷源为多聚磷酸的有机溶液；磷源的浓度为2.5mol/L；磷源的沉积厚度为10μm；4) Liquid-phase deposition of a phosphorus source is performed on the laser-doped silicon wafer, and the deposited phosphorus source covers the front of the silicon wafer; the liquid-phase deposition of the phosphorus source is carried out by roller coating; the phosphorus source is an organic solution of polyphosphoric acid; the concentration of the phosphorus source is 2.5mol/L; the deposition thickness of phosphorus source is 10μm;
5）对完成液相沉积的硅片进行热氧化，使轻重掺区重新分布；热氧化在链式炉或管式炉中实施，氛围为水氧混合气，温度为680℃，时间为50s；5) Thermal oxidation is carried out on the silicon wafer after liquid deposition to redistribute the light and heavy doped areas; thermal oxidation is carried out in a chain furnace or a tube furnace, the atmosphere is a mixture of water and oxygen, the temperature is 680 °C, and the time is 50s;
6）对完成热氧化的硅片进行去PSG和去边结，在0.2wt%浓度HF中反应300s去除PSG和边结；6) Remove PSG and edge junctions on the thermally oxidized silicon wafer, and react in 0.2wt% HF for 300s to remove PSG and edge junctions;
7）对完成去PSG和去边结的硅片进行镀膜，在硅片正面沉积一层起减反射和钝化作用的氮化硅膜；7) Coating the silicon wafer with PSG removal and edge junction removal, and depositing a silicon nitride film for anti-reflection and passivation on the front of the silicon wafer;
8）对完成镀膜的硅片进行丝印和烧结，印刷背电极、背电场和正电极，再进行烧结，电极金属化，得到具有选择性发射极的电池片。8) Screen printing and sintering the coated silicon wafer, printing the back electrode, the back electric field and the positive electrode, and then sintering and metallizing the electrode to obtain a cell with a selective emitter.
对比例3Comparative Example 3
在实施例3的基础上，区别仅在于省去步骤4）和步骤5），其他工艺步骤和工艺条件不变。On the basis of Example 3, the difference is only that step 4) and step 5) are omitted, and other process steps and process conditions remain unchanged.
实施例3所得电池片与对比例3所得电池片的测试对比如表3所示：The test comparison of the obtained cell of Example 3 and the cell of Comparative Example 3 is shown in Table 3:
表3 实施例3所得电池片与对比例3所得电池片的测试对比Table 3 Test comparison of the cell obtained in Example 3 and the cell obtained in Comparative Example 3
Figure dest_path_image003
Figure dest_path_image003
上述各实施例和各对比例所得电池片的测试，其中的掺杂浓度测试，采用的测试设备为Wafer Profiler CVP21，测试标准为GB/T 14146-2009《硅外延层载流子浓度测定 汞探针电容-电压法》；电性能测试，采用的测试设备为HALM测试仪，测试标准为JB/T 9478.3-2013《光电池测量方法 第3部分光电转换效率》。The test of the obtained cells of the above-mentioned embodiments and each comparative example, the test equipment used for the test of the doping concentration is Wafer Profiler CVP21, the test standard is GB/T 14146-2009 "Determination of Carrier Concentration in Silicon Epitaxial Layer - Mercury Probe Capacitance-Voltage Method"; for electrical performance test, the test equipment used is HALM tester, and the test standard is JB/T 9478.3-2013 "Photoelectric Cell Measurement Methods Part 3 Photoelectric Conversion Efficiency".
由上述各实施例、对比例以及表1至表3中的数据对比可知：From above-mentioned each embodiment, comparative example and the data contrast in table 1 to table 3, it can be known:
1）热氧化使结深有所增加，辅助磷源扩散，轻掺区的近表面区活性磷源进一步反应生成PSG，使近表面区磷源浓度下降，开压上升，使最终电性能有所上升。1) Thermal oxidation increases the junction depth, assists the diffusion of the phosphorus source, and the active phosphorus source in the near-surface region of the lightly doped region further reacts to generate PSG, which reduces the concentration of the phosphorus source in the near-surface region and increases the open voltage, which improves the final electrical properties. rise.
2）通过调整磷源种类与浓度，轻掺区的近表面区磷源浓度下降明显，开压提升，使电性能有所提升。2) By adjusting the type and concentration of the phosphorus source, the phosphorus source concentration in the near-surface region of the lightly doped region is significantly reduced, the open voltage is increased, and the electrical performance is improved.
3）通过调整磷源及推进氛围，轻掺区近表面区浓度下降明显，使最终开压提升明显，电性能上升。3) By adjusting the phosphorus source and the propelling atmosphere, the concentration in the near-surface region of the lightly doped region is significantly reduced, so that the final open voltage is significantly improved, and the electrical performance is improved.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the technical principles of the present invention, several improvements and modifications can be made. These improvements and modifications It should also be regarded as the protection scope of the present invention.

Claims (10)

  1. 激光SE电池的制备方法，包括激光掺杂和去PSG，其特征在于，还包括液相沉积磷源和热氧化，在激光掺杂之后，先液相沉积磷源，再热氧化，且热氧化在去PSG之前实施。The preparation method of a laser SE battery includes laser doping and PSG removal, and is characterized in that it also includes liquid deposition of a phosphorus source and thermal oxidation. Implemented before going to PSG.
  2. 根据权利要求1所述的激光SE电池的制备方法，其特征在于，所述液相沉积磷源采用旋涂、喷涂或滚涂。The method for preparing a laser SE battery according to claim 1, wherein the liquid-phase deposition phosphorus source adopts spin coating, spray coating or roller coating.
  3. 根据权利要求2所述的激光SE电池的制备方法，其特征在于，所述磷源为磷酸、P 2O 5或多聚磷酸。 The method for preparing a laser SE battery according to claim 2, wherein the phosphorus source is phosphoric acid, P 2 O 5 or polyphosphoric acid.
  4. 根据权利要求3所述的激光SE电池的制备方法，其特征在于，所述磷源的浓度为0.05～2.5mol/L。The method for preparing a laser SE battery according to claim 3, wherein the concentration of the phosphorus source is 0.05-2.5 mol/L.
  5. 根据权利要求4所述的激光SE电池的制备方法，其特征在于，所述磷源的沉积厚度为0.1～20μm。The method for preparing a laser SE battery according to claim 4, wherein the deposition thickness of the phosphorus source is 0.1-20 μm.
  6. 根据权利要求5所述的激光SE电池的制备方法，其特征在于，所述热氧化在链式炉或管式炉中实施。The method for preparing a laser SE battery according to claim 5, wherein the thermal oxidation is carried out in a chain furnace or a tube furnace.
  7. 根据权利要求6所述的激光SE电池的制备方法，其特征在于，所述热氧化的氛围为氧气、氮氧混合气或水氧混合气。The method for preparing a laser SE battery according to claim 6, wherein the thermal oxidation atmosphere is oxygen, nitrogen-oxygen mixture or water-oxygen mixture.
  8. 根据权利要求7所述的激光SE电池的制备方法，其特征在于，所述热氧化的温度为650～900℃。The method for preparing a laser SE battery according to claim 7, wherein the temperature of the thermal oxidation is 650-900°C.
  9. 根据权利要求8所述的激光SE电池的制备方法，其特征在于，所述热氧化的时间为30s～1h。The method for preparing a laser SE battery according to claim 8, wherein the thermal oxidation time is 30s˜1h.
  10. 根据权利要求9所述的激光SE电池的制备方法，其特征在于，其具体步骤包括：The preparation method of laser SE battery according to claim 9, is characterized in that, its concrete steps comprise:
    1）硅片正面去除损伤层再制绒；1) Remove the damaged layer on the front of the silicon wafer and retexture;
    2）对完成制绒的硅片进行管式扩散；2) Tubular diffusion is performed on the silicon wafers that have finished texturing;
    3）对完成管式扩散的硅片进行激光掺杂；3) Laser doping on the silicon wafer that has completed the tubular diffusion;
    4）对完成激光掺杂的硅片进行液相沉积磷源；4) Liquid-phase deposition of phosphorus source on the laser-doped silicon wafer;
    5）对完成液相沉积的硅片进行热氧化；5) Thermal oxidation of the silicon wafer after liquid deposition;
    6）对完成热氧化的硅片进行去PSG和去边结；6) Remove PSG and edge junction on the thermally oxidized silicon wafer;
    7）对完成去PSG和去边结的硅片进行镀膜；7) Coating the silicon wafers with PSG removal and edge junction removal;
    8）对完成镀膜的硅片进行丝印和烧结。8) Screen printing and sintering the coated silicon wafer.
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