WO2019242242A1 - Procédé de préparation pour une micro- et nano-structure composite de surface d'une cellule monocristalline - Google Patents

Procédé de préparation pour une micro- et nano-structure composite de surface d'une cellule monocristalline Download PDF

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Publication number
WO2019242242A1
WO2019242242A1 PCT/CN2018/118250 CN2018118250W WO2019242242A1 WO 2019242242 A1 WO2019242242 A1 WO 2019242242A1 CN 2018118250 W CN2018118250 W CN 2018118250W WO 2019242242 A1 WO2019242242 A1 WO 2019242242A1
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Prior art keywords
texturing
single crystal
concentration
solution
pickling
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PCT/CN2018/118250
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English (en)
Chinese (zh)
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王涛
洪布双
尹丙伟
杨蕾
张元秋
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通威太阳能（合肥）有限公司
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Publication of WO2019242242A1 publication Critical patent/WO2019242242A1/fr

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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
    • H01L31/0236—Special surface textures
    • H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/08—Etching
    • C30B33/10—Etching in solutions or melts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—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
    • 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 single crystal silicon texturing, in particular to a method for preparing a surface micrometer and nanometer composite structure of a single crystal battery chip.
  • the existing single crystal texturing method while obtaining a lower reflectance (that is, a higher light absorption rate), makes the specific surface area of the silicon wafer larger, increases the surface recombination of minority carriers, and limits Further improvement in efficiency.
  • Black silicon technology is one of the mainstream efficiency improvement technologies currently used on polycrystalline products, and its application on single crystal products is also foreseeable.
  • the production line uses alkaline flock to form pyramid structured flocks for single crystals.
  • Surface its high specific surface area under its low reflectivity limits the further improvement of the texturing effect.
  • FIG. 1 of the specification The steps of a conventional polycrystalline black silicon texturing process are shown in FIG. 1 of the specification. After the texturing process steps, a pile structure as shown in FIG. 3 of the specification can be formed on the black silicon surface; a conventional single crystal The steps of the silicon texturing process are shown in FIG. 2 of the specification. After the texturing process steps, the suede structure shown in FIG. 4 of the specification can be formed on the surface of the single crystal silicon. The reflectivity is still high, making it impossible to improve the light absorption rate, which greatly reduces the photoelectric conversion efficiency of single crystal silicon cells.
  • An object of the present invention is to provide a method for preparing a surface micron nano-composite structure of a single crystal battery chip, so as to solve the problems mentioned in the background art described above.
  • the present invention provides the following technical solutions:
  • a method for preparing a surface micro-nano composite structure of a single crystal battery chip includes the following steps:
  • Alkali texturing solution is used to texturize single crystal battery chips.
  • the alkaline texturing solution is a mixed solution of NaOH, additives and DIW, where the NaOH concentration is 7-9% and the additive concentration is 0.5. -1%, temperature control is 83-87 °C, reaction time is 12-15min, pyramid suede with 15-17% reflectance is formed, and pyramid size is 5-10 ⁇ m;
  • Pickling 1 pickling with HNO3 solution, the HNO3 solution concentration is 0.5-1%, the temperature is controlled to normal temperature, and the pickling time is 60-100s;
  • a texturing solution for single crystal cells is made using an auxiliary texturing solution.
  • the auxiliary texturing solution is a mixed solution of HF, H2O2, silver-containing additives, and DIW.
  • the concentration of HF is 4-5. %
  • H2O2 concentration is 25-30%
  • silver ion content is 0.006-0.01mol / L
  • temperature control is 33-37 ° C
  • reaction time is 150-250s
  • nanometers with a diameter of 80-130nm and a depth of 150-200nm are formed Potholes.
  • step S3 the single crystal battery chip is sequentially desilvered, pickled, and dried.
  • the specific steps are as follows:
  • Desilvering is performed by using a desilvering solution, which is a mixed solution of NH4OH, H2O2, and DIW, wherein the concentration of NH4OH is 0.3-0.5%, the concentration of H2O2 is 3-5%, and the temperature is controlled to normal temperature. , The reaction time is 100-150s;
  • the single crystal battery chip is subjected to DIW cleaning once.
  • the invention combines conventional single-crystal alkali texturing with conventional black silicon-assisted texturing to texture the surface of single crystal silicon to form a micro-nano composite structure suede, and the composite structure suede is under the same specific surface area. Has a higher light absorption rate, and the composite suede structure can be applied to a variety of high-efficiency single crystal silicon battery surfaces, such as PERC, IBC batteries.
  • the invention first performs the first alkaline texturing on the surface of the single crystal silicon to prepare a micron-sized large pyramid structure, and then performs a second silver ion-assisted texturing on this basis to prepare a nano-scale pit-like structure to form
  • the micron-nano composite structure while ensuring a low reflectivity, has a low specific surface area, reduces surface recombination, and further improves the light absorption rate, thereby improving the conversion efficiency of the battery. It is highly practical and worthy of promotion.
  • FIG. 1 is a schematic view of a conventional polycrystalline black silicon texturing process step in the prior art
  • FIG. 2 is a schematic view of a conventional single crystal silicon texturing process step in the prior art
  • FIG. 3 is a schematic view of a structure of a conventional polycrystalline black silicon fleece
  • FIG. 4 is a schematic view of a structure of a conventional single crystal silicon fleece
  • FIG. 5 is a schematic diagram of a single crystal texturing process of the present invention.
  • FIG. 6 is a schematic view of the micron nano-composite structure suede structure of the texturing process of the present invention.
  • FIGS. 1-6 Please refer to FIGS. 1-6.
  • the present invention provides a technical solution:
  • a method for preparing a surface micro-nano composite structure of a single crystal battery chip includes the following steps:
  • Alkali texturing Alkaline texturing solution is used to texturize single crystal battery cells.
  • the alkaline texturing solution is a mixed solution of NaOH, additives and DIW.
  • the additives are all commonly used texturing additives.
  • the NaOH concentration is 7%
  • the additive concentration is 0.5%
  • the temperature is controlled at 83 ° C
  • the reaction time is 12 minutes.
  • a pyramid suede with a reflectance of 15% is formed, and the pyramid size is 5 ⁇ m;
  • Pickling 1 pickling with HNO3 solution, the HNO3 solution concentration is 0.5%, the temperature is controlled to normal temperature, and the pickling time is 60s;
  • Silver ion-assisted texturing texturing of single crystal battery cells using an auxiliary texturing solution, the auxiliary texturing solution is a mixed solution of HF, H2O2, silver-containing additives, and DIW, where the HF concentration is 4%, The H2O2 concentration is 25%, the silver ion content is 0.006mol / L, the temperature is controlled to 33 ° C, and the reaction time is 150s. As shown in FIG. 6 of the specification, nanopits with a diameter of 80nm and a depth of 150nm are formed;
  • the conventional monocrystalline alkali texturing and conventional black silicon texturing are compared with the texturing process steps of the present invention.
  • the conventional black silicon process and the single crystal alkali texturing process are combined, and the single crystal silicon surface is firstly subjected to The first alkaline texturing produced a micron-sized large pyramid structure.
  • a second silver ion-assisted texturing was performed to prepare a nanoscale pit-like structure to form a micron-nano composite structure.
  • the composite suede structure Based on the relatively low specific surface area, the reflectivity of the silicon wafer can be reduced, the light absorption rate can be improved, and the efficiency can be further improved.
  • step S3 the single crystal battery chip is sequentially desilvered, pickled, and dried.
  • the specific steps are as follows:
  • Desilvering using a desilvering solution for desilvering, the desilvering solution is a mixed solution of NH4OH, H2O2, and DIW, wherein the concentration of NH4OH is 0.3%, the concentration of H2O2 is 3%, the temperature is controlled to normal temperature, and the reaction time is 100s;
  • a method for preparing a surface micro-nano composite structure of a single crystal battery chip includes the following steps:
  • Alkali texturing solution is used to texturize single crystal battery chips.
  • the alkaline texturing solution is a mixed solution of NaOH, additives and DIW, where the NaOH concentration is 9% and the additive concentration is 1%.
  • the temperature is controlled at 87 ° C, the reaction time is 15 minutes, a pyramid suede with a reflectance of 17% is formed, and the pyramid size is 10 ⁇ m;
  • Pickling 1 pickling with HNO3 solution, the HNO3 solution concentration is 1%, the temperature is controlled to normal temperature, and the pickling time is 100s;
  • the auxiliary texturing solution is a mixed solution of HF, H2O2, silver-containing additives, and DIW, in which the HF concentration is 5%.
  • H2O2 concentration is 30%
  • silver ion content is 0.01mol / L
  • temperature is controlled at 37 ° C
  • reaction time is 250s
  • nano-pits with a diameter of 130nm and a depth of 200nm are formed;
  • the conventional monocrystalline alkali texturing and conventional black silicon texturing are compared with the texturing process steps of the present invention.
  • the conventional black silicon process and the single crystal alkali texturing process are combined, and the single crystal silicon surface is firstly subjected to The first alkaline texturing produced a micron-sized large pyramid structure.
  • a second silver ion-assisted texturing was performed to prepare a nanoscale pit-like structure to form a micron-nano composite structure.
  • the composite suede structure Based on the relatively low specific surface area, the reflectivity of the silicon wafer can be reduced, the light absorption rate can be improved, and the efficiency can be further improved.
  • step S3 the single crystal battery chip is sequentially desilvered, pickled, and dried.
  • the specific steps are as follows:
  • Desilvering is performed by using a desilvering solution, which is a mixed solution of NH4OH, H2O2, and DIW, wherein the concentration of NH4OH is 0.5%, the concentration of H2O2 is 5%, the temperature is controlled to normal temperature, and the reaction time is 150s;
  • a desilvering solution which is a mixed solution of NH4OH, H2O2, and DIW, wherein the concentration of NH4OH is 0.5%, the concentration of H2O2 is 5%, the temperature is controlled to normal temperature, and the reaction time is 150s;

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

Abstract

La présente invention concerne un procédé de préparation pour une micro- et nano-structure composite de surface d'une cellule monocristalline, comprenant les étapes suivantes : S1, texturation alcaline : former une surface texturée en forme de pyramide ayant la réflectivité de 15 à 17 %, et la taille de la pyramide étant de 5 à 10 µm; S2, décapage à l'acide primaire : réaliser un décapage à l'acide en utilisant une solution de HNO3, la concentration de la solution de HNO3 étant de 0,5 à 1 %, la température étant régulée de façon à être une température ambiante, et une durée du décapage à l'acide étant de 60 à 100 s; S3, texturation assistée par ions d'argent : former un nano-trou ayant un diamètre de 80 à 130 nm et une profondeur de 150 à 200 nm. Selon le procédé, une texturation alcaline monocristalline classique et une texturation assistée par ions d'argent de silicium noir classique sont combinées, et la surface de la cellule monocristalline est texturée pour former une surface texturée de micro- et nano-structure composite, qui a une aire spécifique faible tandis qu'une faible réflectivité est garantie; la recombinaison de surface est réduite, et l'efficacité de conversion d'une cellule est davantage améliorée.
PCT/CN2018/118250 2018-06-20 2018-11-29 Procédé de préparation pour une micro- et nano-structure composite de surface d'une cellule monocristalline WO2019242242A1 (fr)

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CN108807569B (zh) * 2018-06-20 2020-02-14 通威太阳能（合肥）有限公司 一种单晶电池片的表面微米纳米复合结构的制备方法
CN110416353A (zh) * 2019-06-25 2019-11-05 阜宁苏民绿色能源科技有限公司 一种湿法槽式黑硅制绒方法
CN110729379B (zh) * 2019-10-16 2021-05-04 哈尔滨工业大学 一种具有超低反射率微纳复合结构的黑硅衬底制备方法
CN110739357A (zh) * 2019-10-30 2020-01-31 江苏海洋大学 纳米倒金字塔-准微米金字塔背钝化太阳电池及制法
CN112701184A (zh) * 2020-12-16 2021-04-23 天津爱旭太阳能科技有限公司 一种晶硅电池绒面的制作方法
WO2022142943A1 (fr) * 2020-12-30 2022-07-07 泰州隆基乐叶光伏科技有限公司 Procédé et équipement de texturation, tranche de silicium monocristallin et cellule solaire au silicium monocristallin
CN112652671A (zh) * 2020-12-30 2021-04-13 泰州隆基乐叶光伏科技有限公司 制绒方法、单晶硅片及单晶硅太阳电池
CN114551644A (zh) * 2022-02-22 2022-05-27 江西中弘晶能科技有限公司 一种提升高效电池片转换效率的表面微米-纳米复合结构的设计

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CN108807569A (zh) * 2018-06-20 2018-11-13 通威太阳能（合肥）有限公司 一种单晶电池片的表面微米纳米复合结构的制备方法

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