WO2019242242A1 - Preparation method for surface micro and nano composite structure of mono-crystalline cell - Google Patents

Preparation method for surface micro and nano composite structure of mono-crystalline cell Download PDF

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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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texturing
single crystal
concentration
solution
pickling
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PCT/CN2018/118250
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French (fr)
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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    • 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 System
    • 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

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  • 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;

Abstract

A preparation method for a surface micro and nano composite structure of a mono-crystalline cell, comprising the following steps: S1, alkali texturing: forming a pyramid textured surface having the reflectivity of 15-17%, and the size of the pyramid being 5-10 μm; S2, primary acid pickling: performing acid pickling by using a HNO3 solution, the concentration of the HNO3 solution being 0.5-1%, the temperature being controlled to be a room temperature, and a time duration of the acid pickling being 60-100 s; S3, silver ion-assisted texturing: forming a nano hole having a diameter of 80-130 nm and a depth of 150-200 nm. According to the method, a conventional mono-crystalline alkali texturing and conventional black silicon silver ion-assisted texturing are combined, and the surface of the mono-crystalline is textured to form a micro-nano composite structure textured surface, which has a low specific surface area while low reflectivity is ensured; surface recombination is reduced, and conversion efficiency of a cell is further improved.

Description

一种单晶电池片的表面微米纳米复合结构的制备方法Method for preparing surface micron nano composite structure of single crystal battery sheet 技术领域Technical field
本发明涉及单晶硅制绒技术领域，具体为一种单晶电池片的表面微米纳米复合结构的制备方法。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.
背景技术Background technique
现有的单晶制绒方法，在获得较低的反射率(即较高的光吸收率)的同时，使得硅片的比表面积较大，增大了少数载流子的表面复合，限制了效率的进一步提升。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.
黑硅技术是目前多晶产品上使用的主流提效技术之一，其在单晶产品上的应用也是可以预见的，目前产线针对单晶还较多的使用碱制绒形成金字塔结构的绒面，其低反射率下的高比表面积限制了制绒效果的进一步提升。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. At present, 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.
常规的多晶黑硅制绒工艺的步骤如说明书附图1所示，经过该制绒工艺步骤之后，可以在黑硅表面形成了如说明书附图3所示的绒面结构；常规的单晶硅制绒工艺的步骤如说明书附图2所示，经过该制绒工艺步骤之后，可以在单晶硅表面形成了如说明书附图4所示的绒面结构，上述的两种绒面结构，反射率仍然较高，使得光的吸收率无法实现提升，极大的降低了单晶硅电池片的光电转换效率。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.
发明内容Summary of the Invention
本发明的目的在于提供一种单晶电池片的表面微米纳米复合结构的制备方法，以解决上述背景技术中提出的问题。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.
为实现上述目的，本发明提供如下技术方案：To achieve the above objective, the present invention provides the following technical solutions:
一种单晶电池片的表面微米纳米复合结构的制备方法，包括以下步骤：A method for preparing a surface micro-nano composite structure of a single crystal battery chip includes the following steps:
S1、碱制绒：采用碱制绒溶液对单晶电池片进行制绒，所述碱制绒溶液为NaOH、添加剂以及DIW的混合溶液，其中，NaOH浓度为7-9％，添加剂浓度 为0.5-1％，温度控制为83-87℃，反应时间为12-15min，形成反射率为15-17％的金字塔绒面，且金字塔尺寸为5-10μm；S1. Alkali texturing: 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 ℃, reaction time is 12-15min, pyramid suede with 15-17% reflectance is formed, and pyramid size is 5-10μm;
S2、酸洗一：采用HNO3溶液进行酸洗，所述HNO3溶液浓度为0.5-1％，温度控制为常温，酸洗时间为60-100s；S2. 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;
S3、银离子辅助制绒：采用辅助制绒溶液对单晶电池片进行制绒，所述辅助制绒液为HF、H2O2、含银添加剂以及DIW的混合溶液，其中，HF浓度为4-5％，H2O2浓度为25-30％，银离子含量为0.006-0.01mol/L，温度控制为33-37℃，反应时间为150-250s，形成直径为80-130nm、深度为150-200nm的纳米坑洞。S3. Silver ion-assisted texturing: 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.
优选的，在步骤S3完成后，再对单晶电池片依次进行脱银、酸洗二以及烘干，具体步骤如下：Preferably, after step S3 is completed, the single crystal battery chip is sequentially desilvered, pickled, and dried. The specific steps are as follows:
S4、脱银：采用脱银溶液进行脱银，所述脱银溶液为NH4OH、H2O2以及DIW的混合溶液，其中，NH4OH浓度为0.3-0.5％，H2O2浓度为3-5％，温度控制为常温，反应时间为100-150s；S4. Desilvering: 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;
S5、酸洗二：采用HF和HCl的混合溶液进行酸洗，其中，HF和HCl的浓度均在5-8％，温度控制为常温，反应时间为100-150s，使得单晶电池片的反射率控制在3-5％；S5. Pickling 2: Pickling with a mixed solution of HF and HCl, where the concentration of HF and HCl are both 5-8%, the temperature is controlled to normal temperature, and the reaction time is 100-150s, so that the reflection of the single crystal battery chip The rate is controlled at 3-5%;
S6、烘干：将电池片进行烘干处理。S6. Drying: drying the battery sheet.
优选的，步骤S1至步骤S5的每一步完成后，均对单晶电池片进行一次DIW清洗。Preferably, after each step of steps S1 to S5 is completed, the single crystal battery chip is subjected to DIW cleaning once.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
本发明将常规单晶碱制绒与常规黑硅的银离子辅助制绒相结合，对单晶硅表面织构化，形成微米-纳米复合结构绒面，复合结构绒面在相同的比表面积下具有更高的光吸收率，而且此复合绒面结构可以适用于多种高效单晶硅 电池表面，如PERC、IBC电池。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.
本发明先对单晶硅表面先进行了第一次碱制绒，制备出微米级的大金字塔结构，在此基础上进行第二次银离子辅助制绒，制备出纳米级坑状结构，形成微米-纳米复合结构，在保证较低的反射率的同时，具有较低的比表面积，减小表面复合，进一步提高光吸收率，从而提高电池的转换效率，实用性很强，非常值得推广。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.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为现有技术中常规多晶黑硅制绒工艺步骤示意图；1 is a schematic view of a conventional polycrystalline black silicon texturing process step in the prior art;
图2为现有技术中常规单晶硅制绒工艺步骤示意图；2 is a schematic view of a conventional single crystal silicon texturing process step in the prior art;
图3为常规的多晶黑硅制绒的绒面结构示意图；3 is a schematic view of a structure of a conventional polycrystalline black silicon fleece;
图4为常规的单晶硅制绒的绒面结构示意图；FIG. 4 is a schematic view of a structure of a conventional single crystal silicon fleece;
图5为本发明的单晶制绒工艺步骤示意图；5 is a schematic diagram of a single crystal texturing process of the present invention;
图6为本发明的制绒工艺的微米纳米复合结构绒面结构示意图。FIG. 6 is a schematic view of the micron nano-composite structure suede structure of the texturing process of the present invention.
具体实施方式detailed description
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
请参阅图1-6，本发明提供一种技术方案：Please refer to FIGS. 1-6. The present invention provides a technical solution:
实施例一：Embodiment one:
一种单晶电池片的表面微米纳米复合结构的制备方法，如说明书附图5所示，包括以下步骤：A method for preparing a surface micro-nano composite structure of a single crystal battery chip, as shown in FIG. 5 of the specification, includes the following steps:
S1、碱制绒：采用碱制绒溶液对单晶电池片进行制绒，所述碱制绒溶液为NaOH、添加剂以及DIW的混合溶液，添加剂均采用常用的制绒添加剂，其 中，NaOH浓度为7％，添加剂浓度为0.5％，温度控制为83℃，反应时间为12min，如说明书附图6所示，形成反射率为15％的金字塔绒面，且金字塔尺寸为5μm；S1. 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, and the reaction time is 12 minutes. As shown in FIG. 6 of the description, a pyramid suede with a reflectance of 15% is formed, and the pyramid size is 5 μm;
进行一次DIW清洗。Perform a DIW cleaning.
S2、酸洗一：采用HNO3溶液进行酸洗，所述HNO3溶液浓度为0.5％，温度控制为常温，酸洗时间为60s；S2. 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;
进行一次DIW清洗。Perform a DIW cleaning.
S3、银离子辅助制绒：采用辅助制绒溶液对单晶电池片进行制绒，所述辅助制绒液为HF、H2O2、含银添加剂以及DIW的混合溶液，其中，HF浓度为4％，H2O2浓度为25％，银离子含量为0.006mol/L，温度控制为33℃，反应时间为150s，如说明书附图6所示，形成直径为80nm、深度为150nm的纳米坑洞；S3. 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;
进行一次DIW清洗。Perform a DIW cleaning.
常规单晶碱制绒、常规黑硅制绒与本发明的制绒工艺步骤进行对比，本发明中将常规黑硅工艺与单晶碱制绒工艺相结合，先对单晶硅表面先进行了第一次碱制绒，制备出微米级的大金字塔结构，在此基础上进行第二次银离子辅助制绒，制备出纳米级坑状结构，形成微米-纳米复合结构，该复合绒面结构可在相对较低的比表面积基础上，降低硅片的反射率，提高光吸收率，可进一步提高效率。The conventional monocrystalline alkali texturing and conventional black silicon texturing are compared with the texturing process steps of the present invention. In 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. On this basis, 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.
在步骤S3完成后，再对单晶电池片依次进行脱银、酸洗二以及烘干，具体步骤如下：After step S3 is completed, the single crystal battery chip is sequentially desilvered, pickled, and dried. The specific steps are as follows:
S4、脱银：采用脱银溶液进行脱银，所述脱银溶液为NH4OH、H2O2以及DIW的混合溶液，其中，NH4OH浓度为0.3％，H2O2浓度为3％，温度控制为常温，反应时间为100s；S4. 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;
进行一次DIW清洗。Perform a DIW cleaning.
S5、酸洗二：采用HF和HCl的混合溶液进行酸洗，其中，HF和HCl的浓度均在5％，温度控制为常温，反应时间为100s，使得单晶电池片的反射率控制在3％；S5. Pickling 2: Pickled with a mixed solution of HF and HCl, where the concentration of HF and HCl are both 5%, the temperature is controlled to normal temperature, and the reaction time is 100s, so that the reflectance of the single crystal cell is controlled to 3 %
进行一次DIW清洗。Perform a DIW cleaning.
S6、烘干：将电池片进行烘干处理。S6. Drying: drying the battery sheet.
实施例二：Embodiment two:
一种单晶电池片的表面微米纳米复合结构的制备方法，包括以下步骤：A method for preparing a surface micro-nano composite structure of a single crystal battery chip includes the following steps:
S1、碱制绒：采用碱制绒溶液对单晶电池片进行制绒，所述碱制绒溶液为NaOH、添加剂以及DIW的混合溶液，其中，NaOH浓度为9％，添加剂浓度为1％，温度控制为87℃，反应时间为15min，形成反射率为17％的金字塔绒面，且金字塔尺寸为10μm；S1. Alkali texturing: 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 μm;
进行一次DIW清洗。Perform a DIW cleaning.
S2、酸洗一：采用HNO3溶液进行酸洗，所述HNO3溶液浓度为1％，温度控制为常温，酸洗时间为100s；S2. 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;
进行一次DIW清洗。Perform a DIW cleaning.
S3、银离子辅助制绒：采用辅助制绒溶液对单晶电池片进行制绒，所述辅助制绒液为HF、H2O2、含银添加剂以及DIW的混合溶液，其中，HF浓度为5％，H2O2浓度为30％，银离子含量为0.01mol/L，温度控制为37℃，反应时间为250s，形成直径为130nm、深度为200nm的纳米坑洞；S3. Silver ion-assisted texturing: the texturing of single crystal battery cells is performed by using an auxiliary texturing solution. 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, and nano-pits with a diameter of 130nm and a depth of 200nm are formed;
进行一次DIW清洗。Perform a DIW cleaning.
常规单晶碱制绒、常规黑硅制绒与本发明的制绒工艺步骤进行对比，本发明中将常规黑硅工艺与单晶碱制绒工艺相结合，先对单晶硅表面先进行了第一次碱制绒，制备出微米级的大金字塔结构，在此基础上进行第二次银离 子辅助制绒，制备出纳米级坑状结构，形成微米-纳米复合结构，该复合绒面结构可在相对较低的比表面积基础上，降低硅片的反射率，提高光吸收率，可进一步提高效率。The conventional monocrystalline alkali texturing and conventional black silicon texturing are compared with the texturing process steps of the present invention. In 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. On this basis, 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.
在步骤S3完成后，再对单晶电池片依次进行脱银、酸洗二以及烘干，具体步骤如下：After step S3 is completed, the single crystal battery chip is sequentially desilvered, pickled, and dried. The specific steps are as follows:
S4、脱银：采用脱银溶液进行脱银，所述脱银溶液为NH4OH、H2O2以及DIW的混合溶液，其中，NH4OH浓度为0.5％，H2O2浓度为5％，温度控制为常温，反应时间为150s；S4. Desilvering: 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;
进行一次DIW清洗。Perform a DIW cleaning.
S5、酸洗二：采用HF和HCl的混合溶液进行酸洗，其中，HF和HCl的浓度均在8％，温度控制为常温，反应时间为150s，使得单晶电池片的反射率控制在5％；S5. Pickling 2: The mixed solution of HF and HCl is used for pickling. Among them, the concentration of HF and HCl are both 8%, the temperature is controlled to normal temperature, and the reaction time is 150s, so that the reflectance of the single crystal battery is controlled to 5 %
进行一次DIW清洗。Perform a DIW cleaning.
S6、烘干：将电池片进行烘干处理。S6. Drying: drying the battery sheet.
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。Although the embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, and substitutions can be made to these embodiments without departing from the principle and spirit of the present invention. And variations, the scope of the invention is defined by the appended claims and their equivalents.

Claims (3)

  1. 一种单晶电池片的表面微米纳米复合结构的制备方法，其特征在于，包括以下步骤：A method for preparing a surface micron nano-composite structure of a single crystal battery chip is characterized in that it includes the following steps:
    S1、碱制绒：采用碱制绒溶液对单晶电池片进行制绒，所述碱制绒溶液为NaOH、添加剂以及DIW的混合溶液，其中，NaOH浓度为7-9％，添加剂浓度为0.5-1％，温度控制为83-87℃，反应时间为12-15min，形成反射率为15-17％的金字塔绒面，且金字塔尺寸为5-10μm；S1. Alkali texturing: 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 ℃, reaction time is 12-15min, pyramid suede with 15-17% reflectance is formed, and pyramid size is 5-10μm;
    S2、酸洗一：采用HNO3溶液进行酸洗，所述HNO3溶液浓度为0.5-1％，温度控制为常温，酸洗时间为60-100s；S2. 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;
    S3、银离子辅助制绒：采用辅助制绒溶液对单晶电池片进行制绒，所述辅助制绒液为HF、H2O2、含银添加剂以及DIW的混合溶液，其中，HF浓度为4-5％，H2O2浓度为25-30％，银离子含量为0.006-0.01mol/L，温度控制为33-37℃，反应时间为150-250s，形成直径为80-130nm、深度为150-200nm的纳米坑洞。S3. Silver ion-assisted texturing: 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.
  2. 根据权利要求1所述的一种单晶电池片的表面微米纳米复合结构的制备方法，其特征在于，在步骤S3完成后，再对单晶电池片依次进行脱银、酸洗二以及烘干，具体步骤如下：The method of claim 1, wherein after the step S3 is completed, the single crystal battery chip is sequentially desilvered, pickled, and dried. ,Specific steps are as follows:
    S4、脱银：采用脱银溶液进行脱银，所述脱银溶液为NH4OH、H2O2以及DIW的混合溶液，其中，NH4OH浓度为0.3-0.5％，H2O2浓度为3-5％，温度控制为常温，反应时间为100-150s；S4. Desilvering: 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;
    S5、酸洗二：采用HF和HCl的混合溶液进行酸洗，其中，HF和HCl的浓度均在5-8％，温度控制为常温，反应时间为100-150s，使得单晶电池片的反射率控制在3-5％；S5. Pickling 2: Pickling with a mixed solution of HF and HCl, where the concentration of HF and HCl are both 5-8%, the temperature is controlled to normal temperature, and the reaction time is 100-150s, so that the reflection of the single crystal battery chip The rate is controlled at 3-5%;
    S6、烘干：将电池片进行烘干处理。S6. Drying: drying the battery sheet.
  3. 根据权利要求1所述的一种单晶电池片的表面微米纳米复合结构的制 备方法，其特征在于：步骤S1至步骤S5的每一步完成后，均对单晶电池片进行一次DIW清洗。The method for preparing a surface micron nano-composite structure of a single crystal battery cell according to claim 1, characterized in that after each step of steps S1 to S5 is completed, the single crystal battery cell is subjected to DIW cleaning once.
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