WO2014166256A1 - Crystalline silicon solar cell textured structure and manufacturing method for same - Google Patents

Crystalline silicon solar cell textured structure and manufacturing method for same Download PDF

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Publication number
WO2014166256A1
WO2014166256A1 PCT/CN2013/087239 CN2013087239W WO2014166256A1 WO 2014166256 A1 WO2014166256 A1 WO 2014166256A1 CN 2013087239 W CN2013087239 W CN 2013087239W WO 2014166256 A1 WO2014166256 A1 WO 2014166256A1
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solution
solar cell
cleaning
silicon wafer
mol
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PCT/CN2013/087239
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French (fr)
Chinese (zh)
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苏晓东
邹帅
王栩生
章灵军
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苏州阿特斯阳光电力科技有限公司
苏州大学
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Priority to JP2016524403A priority Critical patent/JP6392866B2/en
Publication of WO2014166256A1 publication Critical patent/WO2014166256A1/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
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • the invention relates to a suede structure of a crystalline silicon solar cell and a preparation method thereof, and belongs to the technical field of solar energy.
  • the suede structure on the surface of the silicon wafer can effectively reduce the surface reflectance of the solar cell, and is one of the important factors affecting the photoelectric conversion efficiency of the solar cell.
  • many methods have been tried, including mechanical grooving, laser etching, reactive ion etching (RIE ), chemical etching method (ie wet etching).
  • the mechanical groove method can obtain a lower surface reflectance, but the method causes the mechanical damage of the surface of the silicon wafer to be serious, and the yield thereof is relatively low, so that it is used less in industrial production.
  • RIE reactive ion etching
  • the method can be etched by using different stencils.
  • the etching is generally dry etching, and a so-called 'black silicon' structure can be formed on the surface of the silicon wafer, and the reflectance can be as low as 7.9% or even 4%.
  • the chemical etching method has the characteristics of simple process, low cost and high quality, and compatibility with existing processes, and has become the most used method in the existing industry.
  • the suede structure of a wet-etched crystalline silicon solar cell is generally on the order of micrometers.
  • the current practice is still to further reduce its surface reflectance.
  • Chinese invention patent application CN102610692A Disclosed is a method for preparing a crystalline silicon nano-micron composite suede, which mainly comprises the following steps: (1) cleaning and etching a crystalline silicon wafer to form a micron-sized suede; (2) Uniformly covering a surface of the silicon wafer with a layer of non-continuous nano-sized precious metal particles; (3) selectively etching the surface of the silicon wafer with a chemical etching solution to form a nano-scale suede; (4) The chemical solution removes precious metal particles.
  • the nanometer obtained by the above preparation method - In the micro-composite suede the nanostructure is nano-hole-shaped, that is, its pore diameter is small and the depth is deep. Reports and experiments have shown that the surface reflectance of this composite suede structure is reduced to 12%. The following, but it is not conducive to the surface passivation of the latter, and the conversion efficiency of the cell currently produced by the film is lower than that of the conventionally-made cell of the production line.
  • An object of the present invention is to provide a pile structure of a crystalline silicon solar cell and a method of preparing the same.
  • a crystalline silicon solar cell The preparation method of the suede structure comprises the following steps:
  • the metal ion is selected from one of a gold ion, a silver ion, and a copper ion;
  • the first chemical etching liquid is selected from one of the following mixed solutions: a mixed solution of HF and H 2 O 2 , a mixed solution of HF and HNO 3 , a mixed solution of HF and H 2 CrO 4 ;
  • the concentration of HF is 1 ⁇ 15 mol/L, and the concentration of H 2 O 2 , HNO 3 or H 2 CrO 4 is 0.05 ⁇ 0.5 mol/L;
  • the first cleaning solution is a nitric acid solution having a mass percentage of 27 to 69%, the cleaning time is 60 to 1200 seconds, and the cleaning temperature is 5 ⁇ 85 °C;
  • the second cleaning solution is a hydrofluoric acid solution having a mass percentage of 1 to 10%, the cleaning time is 60 to 600 seconds, and the cleaning temperature is 5 ⁇ 45 °C;
  • the second chemical etching solution is selected from one of the following solutions: a NaOH solution, a KOH solution, a tetramethylammonium hydroxide solution, a mixed solution of HNO 3 and HF acid;
  • reaction temperature is 5 ⁇ 85 °C;
  • the reaction temperature is 5 ⁇ 85 °C;
  • reaction temperature is 5 ⁇ 85 °C;
  • the concentrations of HF and HNO 3 are 0.05-0.5 mol/L and 1-10 mol/L, respectively, the reaction time is 10 ⁇ 1000 seconds, and the reaction temperature is 5 ⁇ 45 °C;
  • the suede structure of the crystalline silicon solar cell can be obtained by washing and drying.
  • the concentration of the nano metal particles in the step (2) is 0.0001 ⁇ 0.1 mol/L. .
  • the immersion time is 10 to 1000 seconds, and the solution temperature is 5 to 85 °C.
  • the etching time of the step (3) is 30 to 3000 seconds, and the reaction temperature is 5 to 45 °C.
  • the present invention simultaneously claims the suede structure of the crystalline silicon solar cell obtained by the above production method.
  • the crystalline silicon solar cell is a polycrystalline silicon solar cell, and the reflectivity of the suede structure is 12% to 20%. .
  • the crystalline silicon solar cell is a monocrystalline silicon solar cell, and the reflectivity of the suede structure is 5% to 15%. .
  • the size of the suede structure of the polycrystalline silicon solar cell prepared by the invention is between 100 and 500 nm, The surface reflectance is between 12 and 20%, and the conversion efficiency of the cell can be improved compared to the nano-micron composite suede structure disclosed in Chinese Patent Application No. CN102610692A. About 0.2 ⁇ 0.5%, it has achieved unexpected results.
  • Nano suede structure of the invention It is more suitable for the manufacturing process of current production line polycrystalline silicon solar cells, which reduces the surface reflectivity without affecting the surface passivation process of the subsequent channels.
  • the working principle of the invention is: on the basis of forming the existing micron-sized suede, firstly coating a layer of uniformly distributed metal nanoparticles on the surface of the silicon wafer; secondly, placing the silicon wafer with metal nanoparticles on the surface thereof;
  • the oxidizing agent H 2 O 2 or HNO 3 or H 2 CrO 4
  • the hydrofluoric acid in the etching liquid oxidizes the silicon wafer.
  • SiO 2 is transported into the solution in the form of fluorosilicic acid.
  • the nearby silicon wafer reacts extremely fast, and the difference in reaction speed will form a line or deep on the surface of the silicon wafer.
  • Hole-shaped microstructure finally, the surface of the silicon wafer is etched and etched using a second chemical etching solution, that is, using an alkali solution (NaOH solution, KOH solution, tetramethylammonium hydroxide solution or mixed acid (HF and HNO 3 ) ))
  • a second chemical etching solution that is, using an alkali solution (NaOH solution, KOH solution, tetramethylammonium hydroxide solution or mixed acid (HF and HNO 3 )
  • Corrosion correction of the above-mentioned linear or deep-hole microstructures the lye is mainly anisotropic etching of the above-mentioned linear or deep-hole microstructures, and the anisotropic corrosion will follow the original Linear or deep-hole microstructure Carried out, will be the result of the original etched linear or deep-like micro
  • This isotropic corrosion is preferentially performed along the original linear or deep-hole microstructures.
  • the etching results in the original linear or deep pores.
  • the microstructure is modified into a nanopore structure with a larger aperture and a shallower depth. Through the modified etching of this step, a nanocrystalline suede of a crystalline silicon solar cell is finally obtained.
  • the present invention has the following advantages compared with the prior art:
  • the invention develops a new method for preparing a suede structure of a crystalline silicon solar cell.
  • the first chemical etching solution is used to etch the surface of the silicon wafer to form a nano-scale suede surface.
  • the second chemical etching solution is used to obtain a suede structure which is more suitable for the crystalline silicon solar cell; the test proves that the size of the suede structure of the polycrystalline silicon solar cell of the present invention is 100 ⁇ 500 nm.
  • the surface reflectance is 12-20%.
  • the conversion efficiency of the cell sheet can be increased by 0.2 to 0.5% with respect to the nano-micron composite suede structure disclosed in Chinese Patent Application No. CN102610692A. Left and right, I have achieved unexpected results.
  • the preparation method of the invention is simple and easy, and has good compatibility with the existing industrial production process, and can be quickly transplanted into industrial production. Suitable for promotion.
  • FIG. 2 is a comparison diagram of reflection spectra of polycrystalline silicon suede prepared by polycrystalline silicon suede and conventional acid etching in the first embodiment of the present invention
  • FIG 3 is a SEM scan of a polycrystalline silicon wafer suede according to a second embodiment of the present invention. (magnification 5K times)
  • Figure 5 is a SEM scan of the polycrystalline silicon wafer suede in the third embodiment of the present invention. (magnification 5K times)
  • FIG. 6 is a comparison diagram of reflection spectra of polycrystalline silicon suede prepared by polycrystalline polystyrene and conventional acid etching in the third embodiment of the present invention.
  • Figure 8 is a SEM scan of the modified etching of the polycrystalline silicon wafer in the fourth embodiment of the present invention. (magnification 50K times)
  • Figure 10 is a SEM scan of the polycrystalline silicon wafer after the modified etching of the second embodiment of the present invention. (magnification 5K times)
  • Figure 11 is a SEM scan of the polycrystalline silicon wafer suede in Comparative Example 2 after uncorrected etching. (zoom in 50K Times)
  • Figure 13 is a SEM scan of the suede of a single crystal silicon wafer in the fifth embodiment of the present invention. (magnification 50K times)
  • Example 14 is a comparison diagram of reflection spectra of single crystal silicon suede after correction etching in Comparative Example 3 and modified etching in Example 5;
  • Figure 15 is a SEM scan of the suede of the single crystal silicon wafer in Comparative Example 3 after the correction etching; (magnification 5K times)
  • Fig. 16 is a SEM scanning view of the suede surface of the single crystal silicon wafer of Comparative Example 3 after uncorrected etching. (zoom in 50K Times)
  • a method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
  • the corrugated layer is corroded to form micron-sized suede; then it is put into AgNO 3 with a concentration of 0.008 mol/L.
  • the reaction was carried out at 20 ° C for 60 s;
  • the suede structure of the polycrystalline silicon solar cell can be obtained by washing and drying.
  • the size of the suede structure of the polycrystalline silicon solar cell obtained in this embodiment is between 100 and 200 nm (as shown in FIG. 1).
  • the average surface reflectance in the wavelength range of 400 ⁇ 1050nm is 13.4%.
  • a method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
  • the suede structure of the polycrystalline silicon solar cell can be obtained by washing and drying.
  • a method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
  • TMAH solution tetramethylammonium hydroxide solution
  • the microstructure of the polycrystalline silicon solar cell obtained in this embodiment has a microstructure of 150 to 300 nm (see FIG. 3).
  • the average surface reflectance in the wavelength range of 400 ⁇ 1050 nm is 12.1%.
  • a method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
  • the microstructure of the polycrystalline silicon solar cell prepared in this embodiment has a microstructure of 150 to 300 nm (see FIG. 5).
  • the average surface reflectance is 10% in the wavelength range of 400 ⁇ 1050 nm.
  • a method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
  • a method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
  • the corrugated layer is corroded to form micron-sized suede; then it is put into AgNO 3 with a concentration of 0.008 mol/L.
  • the reaction was carried out at 20 ° C for 60 s;
  • the suede structure of the polycrystalline silicon solar cell can be obtained by washing and drying.
  • the size of the suede structure of the polycrystalline silicon solar cell after the NaOH solution is etched is 150 ⁇ 300 nm. Between (see Figures 7 and 8), the average surface reflectance is 15.6% in the wavelength range of 400 ⁇ 1050nm (see Figure 9).
  • the nano-sue structure obtained by the modified etching in Comparative Example 2 is a nano-deep-hole structure with a pore size of only about 50 nm (see Figure 10, 11 shows that the average surface reflectance is 5.9% in the wavelength range of 400 ⁇ 1050nm (see Figure 9).
  • the unmodified etching is as in Chinese invention patent application CN102610692A The disclosed method of producing a nano-micron composite suede structure without the modified etching of step (5) above.
  • a method for preparing a nano-sue surface of a single crystal silicon solar cell comprising the following steps:
  • the corrugated layer is corroded to form a micron-sized suede; and then the concentration is 0.008 mol/L.
  • AgNO 3 solution the reaction was carried out at 20 °C for 120 s;
  • a method for preparing a suede structure of a single crystal silicon solar cell comprising the following steps:
  • the corrugated layer is corroded to form a micron-sized suede; and then the concentration is 0.008 mol/L.
  • AgNO 3 solution the reaction was carried out at 20 °C for 120 s;
  • the suede structure of the single crystal silicon solar cell can be obtained by washing and drying.
  • the size of the suede structure of the single crystal silicon solar cell after being etched by the NaOH solution is 150 to 300 nm. Between (see Figures 12 and 13), the average surface reflectance is 6.4% in the wavelength range of 400 ⁇ 1050nm (see Figure 14).
  • the nano-sue structure obtained by the modified etching in Comparative Example 3 is a nano-deep-hole structure with a pore size of only about 50 nm (see Figure 15 16) shows an average surface reflectance of 5.0% in the wavelength range of 400 to 1050 nm (see Figure 14).
  • the unmodified etching is as in Chinese invention patent application CN102610692A The disclosed method of producing a nano-micron composite suede structure without the modified etching of step (5) above.

Abstract

A manufacturing method for a textured structure of a crystalline silicon solar cell, comprising the following steps: (1) cleaning and texturing; (2) immersing a silicon wafer in a solution containing metal ions, such that the surface of the wafer is coated in a layer of metal nanoparticles; (3) corroding the surface of the silicon wafer to form a nanotextured surface; (4) cleaning off the metal particles; (5) immersing in a second chemically corrosive liquid to implement micro-structural corrective etching; (6) cleaning and spin-drying. On the basis of the present method, the size of the manufactured textured structure is 100-500nm, the structure presenting nanometer pores or edged nanometer pyramids or edged nanometer cones or edged nanometer pits of shallow depth and large diameter. The conversion efficiency of the cell is thereby increased.

Description

一种晶体硅太阳能电池的绒面结构及其制备方法Suede structure of crystalline silicon solar cell and preparation method thereof
技术领域 Technical field
本发明涉及一种晶体硅太阳能电池 的绒面结构及其制备方法 ， 属于太阳能技术领域。 The invention relates to a suede structure of a crystalline silicon solar cell and a preparation method thereof, and belongs to the technical field of solar energy.
背景技术 Background technique
随着太阳能电池组件的广泛应用，光伏发电在新能源中越来越占有重要比例，获得了飞速发展。目前商业化的太阳电池产品中，晶体硅（单晶和多晶）太阳电池的市场份额最大，一直保持 85% 以上的市场占有率。 With the wide application of solar modules, photovoltaic power generation has become an increasingly important part of new energy sources and has achieved rapid development. Among the current commercial solar cell products, crystalline silicon (single crystal and polycrystalline) solar cells have the largest market share and have remained More than 85% market share.
目前，在太阳电池的生产工艺中，硅片表面的绒面结构可以有效地降低太阳电池的表面反射率，是影响太阳电池光电转换效率的重要因素之一。为了在晶体硅太阳能电池表面获得好的绒面结构，以达到较好的减反射效果，人们尝试了许多方法，常用的包括机械刻槽法、激光刻蚀法、反应离子刻蚀法（ RIE ）、化学腐蚀法（即湿法腐蚀）等。其中，机械刻槽方法可以得到较低的表面反射率，但是该方法造成硅片表面的机械损伤比较严重，而且其成品率相对较低，故而在工业生产中使用较少。对于激光刻蚀法，是用激光制作不同的刻槽花样，条纹状和倒金字塔形状的表面都已经被制作出来，其反射率可以低至 8.3% ，但是由其制得的电池的效率都比较低，不能有效地用于生产。 RIE 方法可以利用不同的模版来进行刻蚀，刻蚀一般是干法刻蚀，可以在硅片表面形成所谓的'黑硅'结构，其反射率可以低至 7.9% ，甚至可以达到 4% ，但是由于设备昂贵，生产成本较高，因此在工业成产中使用较少。而化学腐蚀法具有工艺简单、廉价优质、和现有工艺好兼容等特点，成为了现有工业中使用最多的方法。 At present, in the production process of solar cells, the suede structure on the surface of the silicon wafer can effectively reduce the surface reflectance of the solar cell, and is one of the important factors affecting the photoelectric conversion efficiency of the solar cell. In order to obtain a good suede structure on the surface of a crystalline silicon solar cell to achieve better anti-reflection effect, many methods have been tried, including mechanical grooving, laser etching, reactive ion etching ( RIE ), chemical etching method (ie wet etching). Among them, the mechanical groove method can obtain a lower surface reflectance, but the method causes the mechanical damage of the surface of the silicon wafer to be serious, and the yield thereof is relatively low, so that it is used less in industrial production. For the laser etching method, different groove patterns are made by laser, and the stripe-shaped and inverted pyramid-shaped surfaces have been fabricated, and the reflectance can be as low as 8.3%, but the battery produced by it is relatively inefficient and cannot be effectively used in production. RIE The method can be etched by using different stencils. The etching is generally dry etching, and a so-called 'black silicon' structure can be formed on the surface of the silicon wafer, and the reflectance can be as low as 7.9% or even 4%. However, due to the high cost of equipment and high production costs, it is used less in industrial production. The chemical etching method has the characteristics of simple process, low cost and high quality, and compatibility with existing processes, and has become the most used method in the existing industry.
目前，采用湿法腐蚀的晶体硅太阳能电池的绒面结构一般呈微米级。目前的常规做法仍是进一步降低其表面反射率。中国发明专利申请 CN102610692A 公开了一种晶体硅纳米 - 微米复合绒面的制备方法，其主要包括如下步骤： (1) 将晶硅硅片进行清洗、腐蚀制绒，形成微米级绒面； (2) 在硅片表面均匀覆盖一层非连续纳米级贵金属粒子； (3) 用化学腐蚀液选择性腐蚀硅片表面，形成纳米级绒面； (4) 化学溶液去除贵金属粒子。然而，上述制备方法得到的纳米 - 微米复合绒面中，其纳米结构是呈纳米孔状，即其孔径较小、而深度较深。文献报道及试验证明，这种复合绒面结构的表面反射率虽然降低至 12% 以下，但却不利于后道的表面钝化，且目前由其制得的电池片转换效率要低于产线常规制绒的电池片。 At present, the suede structure of a wet-etched crystalline silicon solar cell is generally on the order of micrometers. The current practice is still to further reduce its surface reflectance. Chinese invention patent application CN102610692A Disclosed is a method for preparing a crystalline silicon nano-micron composite suede, which mainly comprises the following steps: (1) cleaning and etching a crystalline silicon wafer to form a micron-sized suede; (2) Uniformly covering a surface of the silicon wafer with a layer of non-continuous nano-sized precious metal particles; (3) selectively etching the surface of the silicon wafer with a chemical etching solution to form a nano-scale suede; (4) The chemical solution removes precious metal particles. However, the nanometer obtained by the above preparation method - In the micro-composite suede, the nanostructure is nano-hole-shaped, that is, its pore diameter is small and the depth is deep. Reports and experiments have shown that the surface reflectance of this composite suede structure is reduced to 12%. The following, but it is not conducive to the surface passivation of the latter, and the conversion efficiency of the cell currently produced by the film is lower than that of the conventionally-made cell of the production line.
发明内容 Summary of the invention
本发明目的是提供一种晶体硅太阳能电池 的绒面结构及其制备方法。 SUMMARY OF THE INVENTION An object of the present invention is to provide a pile structure of a crystalline silicon solar cell and a method of preparing the same.
为达到上述目的，本发明采用的技术方案是： 一种 晶体硅太阳能电池 的绒面结构的制备方法，包括如下步骤： In order to achieve the above object, the technical solution adopted by the present invention is: A crystalline silicon solar cell The preparation method of the suede structure comprises the following steps:
(1) 将多晶硅硅片进行清洗、腐蚀制绒，形成微米级绒面； (1) cleaning and etching the polycrystalline silicon wafer to form micron-sized suede;
(2) 将上述硅片放入含有金属离子的溶液中浸泡，使硅片表面涂覆一层金属纳米颗粒； (2) immersing the above silicon wafer in a solution containing metal ions to coat a surface of the silicon wafer with a layer of metal nanoparticles;
所述金属离子选自金离子、银离子和铜离子中的一种； The metal ion is selected from one of a gold ion, a silver ion, and a copper ion;
(3) 用第一化学腐蚀液腐蚀硅片表面，形成纳米级绒面； (3) etching the surface of the silicon wafer with a first chemical etching solution to form a nano-scale suede;
所述第一化学腐蚀液选自以下混合溶液中的一种： HF 与 H2O2 的混合溶液、 HF 与 HNO3 的混合溶液、 HF 与 H2CrO4 的混合溶液；The first chemical etching liquid is selected from one of the following mixed solutions: a mixed solution of HF and H 2 O 2 , a mixed solution of HF and HNO 3 , a mixed solution of HF and H 2 CrO 4 ;
其中， HF 的浓度为 1~15 mol/L ， H2O2 、 HNO3 或 H2CrO4 的浓度为 0.05~0.5 mol/L ；The concentration of HF is 1~15 mol/L, and the concentration of H 2 O 2 , HNO 3 or H 2 CrO 4 is 0.05~0.5 mol/L;
(4) 分别用第一清洗液、第二清洗液、去离子水清洗上述硅片，去除金属颗粒； (4) cleaning the silicon wafer with the first cleaning solution, the second cleaning solution, and deionized water, respectively, to remove the metal particles;
所述第一清洗液 为质量百分比为 27~69% 的硝酸溶液，清洗时间为 60~1200 秒，清洗温度为 5~85℃ ； The first cleaning solution is a nitric acid solution having a mass percentage of 27 to 69%, the cleaning time is 60 to 1200 seconds, and the cleaning temperature is 5~85 °C;
所述第二清洗液 为质量百分比为 1~10% 的氢氟酸溶液，清洗时间为 60~600 秒，清洗温度为 5~45℃ ； The second cleaning solution is a hydrofluoric acid solution having a mass percentage of 1 to 10%, the cleaning time is 60 to 600 seconds, and the cleaning temperature is 5~45 °C;
(5) 将上述硅片放入第二化学腐蚀液中 进行微结构修正刻蚀； (5) placing the above silicon wafer into the second chemical etching solution for microstructure modification etching;
所述 第二化学腐蚀液选自以下溶液中的一种： NaOH 溶液、 KOH 溶液、四甲基氢氧化铵溶液、 HNO3 与 HF 酸的混合溶液；The second chemical etching solution is selected from one of the following solutions: a NaOH solution, a KOH solution, a tetramethylammonium hydroxide solution, a mixed solution of HNO 3 and HF acid;
当选自 NaOH 溶液时，其浓度为 0.001~0.1 mol/L ，反应时间为 10~1000 秒，反应温度为 5~85℃ ； When selected from NaOH solution, its concentration is 0.001~0.1 mol/L, and the reaction time is 10~1000. Seconds, the reaction temperature is 5~85 °C;
当选自 KOH 溶液时，其浓度为 0.001~0.1 mol/L ，反应时间为 10~1000 秒，反应温度为 5~85℃ ； When selected from KOH solution, its concentration is 0.001~0.1 mol/L, and the reaction time is 10~1000. Seconds, the reaction temperature is 5~85 °C;
当选自四甲基氢氧化铵溶液时，其浓度为 0.001~0.1 mol/L ，反应时间为 10~1000 秒，反应温度为 5~85℃ ； When selected from tetramethylammonium hydroxide solution, its concentration is 0.001~0.1 mol/L, and the reaction time is 10~1000. Seconds, the reaction temperature is 5~85 °C;
当选自 HNO3 与 HF 酸的混合溶液时， HF 与 HNO3 的浓度分别为 0.05~0.5 mol/L 、 1~10 mol/L ，反应时间为 10~1000 秒，反应温度为 5~45℃ ；When selected from a mixed solution of HNO 3 and HF acid, the concentrations of HF and HNO 3 are 0.05-0.5 mol/L and 1-10 mol/L, respectively, the reaction time is 10~1000 seconds, and the reaction temperature is 5~45 °C;
(6) 清洗、甩干，即可得到所述 晶体硅太阳能电池 的绒面结构。 (6) The suede structure of the crystalline silicon solar cell can be obtained by washing and drying.
上述技术方案中，所述步骤 (2) 中的纳米级金属颗粒的浓度为 0.0001~0.1 mol/L 。 In the above technical solution, the concentration of the nano metal particles in the step (2) is 0.0001~0.1 mol/L. .
上述技术方案中，所述步骤 (2) 中，浸泡时间为 10~1000 秒，溶液温度为 5~85℃ 。 In the above technical solution, in the step (2), the immersion time is 10 to 1000 seconds, and the solution temperature is 5 to 85 °C.
上述技术方案中，所述步骤 (3) 的腐蚀时间为 30~3000 秒，反应温度为 5~45℃ 。 In the above technical solution, the etching time of the step (3) is 30 to 3000 seconds, and the reaction temperature is 5 to 45 °C.
本发明同时请求保护由上述制备方法得到的 晶体硅太阳能电池 的绒面结构。 The present invention simultaneously claims the suede structure of the crystalline silicon solar cell obtained by the above production method.
上述技术方案中，所述 晶体硅太阳能电池为多晶硅太阳能电池，其 绒面结构的反射率为 12%~20% 。 In the above technical solution, the crystalline silicon solar cell is a polycrystalline silicon solar cell, and the reflectivity of the suede structure is 12% to 20%. .
上述技术方案中，所述 晶体硅太阳能电池为单晶硅太阳能电池，其 绒面结构的反射率为 5%~15% 。 In the above technical solution, the crystalline silicon solar cell is a monocrystalline silicon solar cell, and the reflectivity of the suede structure is 5% to 15%. .
经测试，本发明制备得到的多晶硅太阳能电池的绒面结构的 大小在 100~500 nm 之间，其 表面反射率在 12~20% 之间，相对于中国发明专利申请 CN102610692A 公开的纳米 - 微米复合绒面结构，其电池片的转换效率可提高 0.2~0.5% 左右，取得了意想不到的效果。本发明的纳米绒面结构 更适合于目前产线多晶硅太阳能电池的制造工艺，在降低表面反射率的同时又不影响后道的表面钝化工艺。 The size of the suede structure of the polycrystalline silicon solar cell prepared by the invention is between 100 and 500 nm, The surface reflectance is between 12 and 20%, and the conversion efficiency of the cell can be improved compared to the nano-micron composite suede structure disclosed in Chinese Patent Application No. CN102610692A. About 0.2~0.5%, it has achieved unexpected results. Nano suede structure of the invention It is more suitable for the manufacturing process of current production line polycrystalline silicon solar cells, which reduces the surface reflectivity without affecting the surface passivation process of the subsequent channels.
本发明的工作 原理是：在形成现有的微米级绒面的基础上，先在硅片表面反应涂覆一层分布均匀的金属纳米颗粒；其次将表面分布着金属纳米颗粒的硅片放入到第一化学腐蚀液中，腐蚀液中的氧化剂（ H2O2 或 HNO3 或 H2CrO4 ）起氧化硅片的作用；同时，腐蚀液中的氢氟酸再将硅片氧化生成的 SiO2 以氟硅酸的形式输运到溶液中，而在金属颗粒催化的作用下，其附近的硅片反应极快，由于反应速度之间的差异就会在硅片表面形成线状或深孔状的微结构；最后，再利用第二化学腐蚀溶液对硅片表面进行修正刻蚀，即利用碱液（ NaOH 溶液、 KOH 溶液、四甲基氢氧化铵溶液或混合酸（ HF 和 HNO3 ））对上述制得线状或深孔状的微结构进行腐蚀修正，碱液主要是对上述线状或深孔状微结构进行各向异性腐蚀，这种各向异性腐蚀会沿着原来的线状或深孔状微结构优先进行，刻蚀结果就会使原来的线状或深孔状微结构被修正成带有棱角的纳米金字塔或纳米椎体或纳米坑状结构，而混合酸（ HF 和 HNO3 ）主要是对上述线状或深孔状微结构进行各向同性腐蚀，这种各向同性腐蚀会沿着原来的线状或深孔状微结构优先进行，刻蚀结果就会使原来的线状或深孔状微结构被修正成孔径较大，深度较浅的纳米孔状结构，通过该步的修正刻蚀最终制得较优的晶硅太阳电池纳米绒面。The working principle of the invention is: on the basis of forming the existing micron-sized suede, firstly coating a layer of uniformly distributed metal nanoparticles on the surface of the silicon wafer; secondly, placing the silicon wafer with metal nanoparticles on the surface thereof; In the first chemical etching solution, the oxidizing agent (H 2 O 2 or HNO 3 or H 2 CrO 4 ) in the etching solution functions as a silicon oxide sheet; at the same time, the hydrofluoric acid in the etching liquid oxidizes the silicon wafer. SiO 2 is transported into the solution in the form of fluorosilicic acid. Under the action of the metal particles, the nearby silicon wafer reacts extremely fast, and the difference in reaction speed will form a line or deep on the surface of the silicon wafer. Hole-shaped microstructure; finally, the surface of the silicon wafer is etched and etched using a second chemical etching solution, that is, using an alkali solution (NaOH solution, KOH solution, tetramethylammonium hydroxide solution or mixed acid (HF and HNO 3 ) )) Corrosion correction of the above-mentioned linear or deep-hole microstructures, the lye is mainly anisotropic etching of the above-mentioned linear or deep-hole microstructures, and the anisotropic corrosion will follow the original Linear or deep-hole microstructure Carried out, will be the result of the original etched linear or deep-like microstructures are modified into a pyramid having nano or nano angular vertebral structure or nano-pits, and a mixed acid (HF and HNO 3) above is mainly Linear or deep-hole microstructures undergo isotropic etching. This isotropic corrosion is preferentially performed along the original linear or deep-hole microstructures. The etching results in the original linear or deep pores. The microstructure is modified into a nanopore structure with a larger aperture and a shallower depth. Through the modified etching of this step, a nanocrystalline suede of a crystalline silicon solar cell is finally obtained.
由于上述技术方案的采用，与现有技术相比，本发明具有如下优点： Due to the adoption of the above technical solutions, the present invention has the following advantages compared with the prior art:
1 ．本发明开发了一种新的晶体硅太阳能电池的绒面结构的制备方法，其在现有的微米级绒面结构的基础上，采用第一化学腐蚀液腐蚀硅片表面，形成纳米级绒面，清洗后进一步采用第二化学腐蚀液中 进行微结构修正刻蚀，得到了更适用于晶体硅太阳能电池的绒面结构；试验证明：本发明的多晶硅太阳能电池的 绒面结构的 大小在 100~500 nm 之间，呈孔径较大，深度较浅的纳米孔状或带有棱角的纳米金字塔或带有棱角纳米椎体或带有棱角的纳米坑状结构，其 表面反射率在 12~20% 之间，相对于中国发明专利申请 CN102610692A 公开的纳米 - 微米复合绒面结构，其电池片的转换效率可提高 0.2~0.5% 左右，取得了意想不到的效果。 1 . The invention develops a new method for preparing a suede structure of a crystalline silicon solar cell. On the basis of the existing micron-sized suede structure, the first chemical etching solution is used to etch the surface of the silicon wafer to form a nano-scale suede surface. After cleaning, further use the second chemical etching solution The microstructure modification etching is performed to obtain a suede structure which is more suitable for the crystalline silicon solar cell; the test proves that the size of the suede structure of the polycrystalline silicon solar cell of the present invention is 100~500 nm. Between the nanoporous or angular pyramids or the nano-pit structures with angular nano-vertex or angular corners, the surface reflectance is 12-20%. The conversion efficiency of the cell sheet can be increased by 0.2 to 0.5% with respect to the nano-micron composite suede structure disclosed in Chinese Patent Application No. CN102610692A. Left and right, I have achieved unexpected results.
2 ．本发明 的制备方法简单易行， 与现有工业化生产工艺兼容性较好，可以快速移植到工业化生产中 ，适于推广应用。 2 . The preparation method of the invention is simple and easy, and has good compatibility with the existing industrial production process, and can be quickly transplanted into industrial production. Suitable for promotion.
附图说明 DRAWINGS
图 1 是本发明实施例一中多晶硅硅片绒面的 SEM 扫描图； （放大 5K 倍） 1 is a SEM scan of a polycrystalline silicon wafer suede according to a first embodiment of the present invention; (magnification 5K times)
图 2 是本发明实施例一中多晶硅绒面与常规酸腐蚀制备的多晶硅绒面的反射光谱对比图； 2 is a comparison diagram of reflection spectra of polycrystalline silicon suede prepared by polycrystalline silicon suede and conventional acid etching in the first embodiment of the present invention;
图 3 是本发明实施例二中多晶硅硅片绒面的 SEM 扫描图；（放大 5K 倍） 3 is a SEM scan of a polycrystalline silicon wafer suede according to a second embodiment of the present invention; (magnification 5K times)
图 4 是本发明实施例二中多晶硅绒面与常规酸腐蚀制备的多晶硅绒面的反射光谱对比图； 4 is a comparison diagram of reflection spectra of polycrystalline silicon suede prepared by polycrystalline silicon suede and conventional acid etching in the second embodiment of the present invention;
图 5 是本发明实施例三中多晶硅硅片绒面的 SEM 扫描图；（放大 5K 倍） Figure 5 is a SEM scan of the polycrystalline silicon wafer suede in the third embodiment of the present invention; (magnification 5K times)
图 6 是本发明实施例三中多晶硅绒面与常规酸腐蚀制备的多晶硅绒面的反射光谱对比图； 6 is a comparison diagram of reflection spectra of polycrystalline silicon suede prepared by polycrystalline polystyrene and conventional acid etching in the third embodiment of the present invention;
图 7 是本发明实施例四中多晶硅硅片绒面的 SEM 扫描图；（放大 5K 倍） 7 is a SEM scan of a polycrystalline silicon wafer suede according to a fourth embodiment of the present invention; (magnification 5K times)
图 8 是本发明 实施例四 中多晶硅硅片绒面进行修正刻蚀的 SEM 扫描图；（放大 50K 倍） Figure 8 is a SEM scan of the modified etching of the polycrystalline silicon wafer in the fourth embodiment of the present invention; (magnification 50K times)
图 9 是本发明对比例二中未进行修正刻蚀与实施例四进行修正刻蚀后的多晶硅绒面的反射光谱对比图； 9 is a comparison diagram of reflection spectra of polycrystalline silicon suede after the modified etching in Comparative Example 2 and the modified etching in the fourth embodiment;
图 10 是本发明对比例二中多晶硅硅片绒面未进行修正刻蚀后的 SEM 扫描图；（放大 5K 倍） Figure 10 is a SEM scan of the polycrystalline silicon wafer after the modified etching of the second embodiment of the present invention; (magnification 5K times)
图 11 是本发明对比例二中多晶硅硅片绒面进行未进行修正刻蚀后的 SEM 扫描图。（放大 50K 倍） Figure 11 is a SEM scan of the polycrystalline silicon wafer suede in Comparative Example 2 after uncorrected etching. (zoom in 50K Times)
图 12 是本发明实施例五中单晶硅硅片绒面的 SEM 扫描图；（放大 5K 倍） 12 is a SEM scan of a suede surface of a single crystal silicon wafer according to a fifth embodiment of the present invention; (magnification 5K times)
图 13 是本发明实施例五中单晶硅硅片绒面的 SEM 扫描图；（放大 50K 倍） Figure 13 is a SEM scan of the suede of a single crystal silicon wafer in the fifth embodiment of the present invention; (magnification 50K times)
图 14 是本发明对比例三中未进行修正刻蚀与实施例五进行修正刻蚀后的单晶硅绒面的反射光谱对比图； 14 is a comparison diagram of reflection spectra of single crystal silicon suede after correction etching in Comparative Example 3 and modified etching in Example 5;
图 15 是本发明对比例三中单晶硅硅片绒面未进行修正刻蚀后的 SEM 扫描图；（放大 5K 倍） Figure 15 is a SEM scan of the suede of the single crystal silicon wafer in Comparative Example 3 after the correction etching; (magnification 5K times)
图 16 是本发明对比例三中单晶硅硅片绒面进行未进行修正刻蚀后的 SEM 扫描图。（放大 50K 倍） Fig. 16 is a SEM scanning view of the suede surface of the single crystal silicon wafer of Comparative Example 3 after uncorrected etching. (zoom in 50K Times)
具体实施方式 detailed description
下面 结合实施例对本发明作进一步描述： The present invention will be further described below in conjunction with the embodiments:
实施例一 Embodiment 1
一种多晶硅太阳电池的绒面结构的制备方法，包括如下步骤： A method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
(1) 将厚度为 180±10μm ，大小为 156mm ×156mm 的 P 型多晶硅片损伤层去除并清洗干净后， 腐蚀制绒，形成微米级绒面；然后 投入到浓度为 0.008mol/L 的 AgNO3 溶液中，于 20 ℃ 条件下反应 60 s ；(1) After removing and cleaning the damaged layer of P-type polycrystalline silicon wafer with a thickness of 180±10μm and a size of 156mm × 156mm, the corrugated layer is corroded to form micron-sized suede; then it is put into AgNO 3 with a concentration of 0.008 mol/L. In the solution, the reaction was carried out at 20 ° C for 60 s;
(2) 将上步完成后的硅片放入 HF 与 H2O2 的混合溶液中，其浓度分别为 3mol/L ， 0.1mol/L ，于 20 ℃ 条件下反应 300 s ；(2) The silicon wafer after the completion of the above step is placed in a mixed solution of HF and H 2 O 2 at a concentration of 3 mol/L and 0.1 mol/L, respectively, and reacted at 20 ° C for 300 s;
(3) 将上步完成后的硅片放入质量百分比为 69% 硝酸溶液中清洗 300 s ，清洗温度为 20 ℃ ； (3) The silicon wafer after the previous step is placed in a 69% nitric acid solution for 300 s, and the cleaning temperature is 20 °C. ;
(4) 将上步完成后的硅片放入质量百分比为 5% 氢氟溶液中清洗 200 s ，清洗温度为 20 ℃ ； (4) Put the silicon wafer after the previous step into a 5% hydrogen fluoride solution for 200 s and the cleaning temperature is 20 °C. ;
(5) 将上步完成后的硅片放入 0.05mol/L 的 KOH 溶液中，于 20 ℃ 条件下反应 300s ； (5) Put the silicon wafer after the previous step into 0.05mol/L KOH solution and react at 20 °C. 300s ;
(6) 清洗、甩干，即可得到所述 多晶硅 太阳能电池的绒面结构。 (6) The suede structure of the polycrystalline silicon solar cell can be obtained by washing and drying.
本实施例所制得的多晶硅太阳电池的绒面结构的尺寸在 100~200nm 之间（见图 1 所示），在 400~1050nm 波长范围内其表面平均反射率为 13.4% 。 The size of the suede structure of the polycrystalline silicon solar cell obtained in this embodiment is between 100 and 200 nm (as shown in FIG. 1). The average surface reflectance in the wavelength range of 400~1050nm is 13.4%.
对比例一 Comparative example one
一种多晶硅太阳电池的绒面结构的制备方法，包括如下步骤： A method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
(1) 将厚度为 180±10μm ，大小为 156mm ×156mm 的 P 型多晶硅片损伤层去除并清洗干净后， 腐蚀制绒，形成微米级绒面； (1) P with a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm After the damaged layer of the polycrystalline silicon wafer is removed and cleaned, the fleece is corroded to form a micron-sized suede;
(2) 清洗、甩干，即可得到所述 多晶硅 太阳能电池的绒面结构。 (2) The suede structure of the polycrystalline silicon solar cell can be obtained by washing and drying.
实施例一中多晶硅绒面与对比例一中常规酸腐蚀制备的多晶硅绒面的反射光谱对比图参见 图 2 所示。 A comparison of the reflection spectra of the polycrystalline silicon suede prepared in the first embodiment and the conventional acid etching in Comparative Example 1 is shown in Fig. 2.
实施例二 Embodiment 2
一种多晶硅太阳电池的绒面结构的制备方法，包括如下步骤： A method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
（ 1 ）将厚度为 180±10μm ，大小为 156mm ×156mm 的 P 型多晶硅片损伤层去除并清洗干净后， 腐蚀制绒，形成微米级绒面； (1) P with a thickness of 180±10μm and a size of 156mm × 156mm After the damaged layer of the polycrystalline silicon wafer is removed and cleaned, the fleece is corroded to form a micron-sized suede;
然后投入到浓度为 0.008mol/L 的 AgNO3 溶液中，于 20 ℃ 条件下反应 60s ；Then, it was put into AgNO 3 solution with a concentration of 0.008 mol/L and reacted at 20 °C for 60 s.
（ 2 ）将上步完成后的硅片放入 HF 与 H2O2 的混合溶液中，其浓度分别为 3mol/L ， 0.1mol/L ，于 20 ℃ 条件下反应 300s ；(2) The silicon wafer after the completion of the above step is placed in a mixed solution of HF and H 2 O 2 at a concentration of 3 mol/L and 0.1 mol/L, respectively, and reacted at 20 ° C for 300 s;
（ 3 ）将上步完成后的硅片放入质量百分比为 69% 硝酸溶液中清洗 300s ，清洗温度为 20 ℃ ； (3) The silicon wafer after the completion of the above step is placed in a mass percentage of 69% nitric acid solution for 300 s, and the cleaning temperature is 20 °C. ;
（ 4 ）将上步完成后的硅片放入质量百分比为 5% 氢氟溶液中清洗 200s ，清洗温度为 20 ℃ ； (4) The silicon wafer after the completion of the previous step is placed in a mass percentage of 5% hydrofluoric solution for 200 s, and the cleaning temperature is 20 °C. ;
（ 5 ）将上步完成后的硅片放入 0.025mol/L 的四甲基氢氧化铵溶液（ TMAH 溶液）中，于 20 ℃ 条件下反应 300s ； (5) Put the silicon wafer after the previous step into 0.025mol/L tetramethylammonium hydroxide solution (TMAH solution), The reaction was carried out at 20 °C for 300 s ;
（ 6 ）将上步完成后的硅片用去离子水冲洗干净并甩干。 (6) Rinse the silicon wafer after the completion of the previous step with deionized water and dry it.
本实施例所制得的多晶硅太阳电池绒面微结构尺寸在 150~300 nm 之间（见图 3 所示），在 400~1050 nm 的波长范围内其表面平均反射率为 12.1% 。 The microstructure of the polycrystalline silicon solar cell obtained in this embodiment has a microstructure of 150 to 300 nm (see FIG. 3). The average surface reflectance in the wavelength range of 400~1050 nm is 12.1%.
实施例二中多晶硅绒面与对比例一中常规酸腐蚀制备的多晶硅绒面的反射光谱对比图参见 图 4 所示。 The comparison of the reflection spectra of the polycrystalline silicon suede prepared in the second embodiment and the conventional acid etching in Comparative Example 1 is shown in Fig. 4.
实施例三 Embodiment 3
一种多晶硅太阳电池的绒面结构的制备方法，包括如下步骤： A method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
(1) 将厚度为 180±10μm ，大小为 156mm ×156mm 的 P 型多晶硅片损伤层去除并清洗干净后， 腐蚀制绒，形成微米级绒面； (1) P with a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm After the damaged layer of the polycrystalline silicon wafer is removed and cleaned, the fleece is corroded to form a micron-sized suede;
然后投入到浓度为 0.008mol/L 的 AgNO3 溶液中，于 20 ℃ 条件下反应 60s ；Then, it was put into AgNO 3 solution with a concentration of 0.008 mol/L and reacted at 20 °C for 60 s.
（ 2 ）将上步完成后的硅片放入 HF 与 H2O2 的混合溶液中，其浓度分别为 3mol/L ， 0.1mol/L ，于 20 ℃ 条件下反应 300s ；(2) The silicon wafer after the completion of the above step is placed in a mixed solution of HF and H 2 O 2 at a concentration of 3 mol/L and 0.1 mol/L, respectively, and reacted at 20 ° C for 300 s;
（ 3 ）将上步完成后的硅片放入质量百分比为 69% 硝酸溶液中清洗 300s ，清洗温度为 20 ℃ ； (3) The silicon wafer after the completion of the above step is placed in a mass percentage of 69% nitric acid solution for 300 s, and the cleaning temperature is 20 °C. ;
（ 4 ）将上步完成后的硅片放入质量百分比为 5% 氢氟溶液中清洗 200s ，清洗温度为 20 ℃ ； (4) The silicon wafer after the completion of the previous step is placed in a mass percentage of 5% hydrofluoric solution for 200 s, and the cleaning temperature is 20 °C. ;
（ 5 ）将上步完成后的硅片放入 HF 与 HNO3 的混合溶液种，其浓度分别为 0.1mol/L ， 5mol/L ，于 20 ℃ 条件下反应 150s ；(5) The silicon wafer after the completion of the above step is placed in a mixed solution of HF and HNO 3 at a concentration of 0.1 mol/L and 5 mol/L, respectively, and reacted at 20 ° C for 150 s;
（ 6 ）将上步完成后的硅片用去离子水冲洗干净并甩干。 (6) Rinse the silicon wafer after the completion of the previous step with deionized water and dry it.
本实施例所制得的多晶硅太阳电池绒面微结构尺寸在 150~300nm 之间（见图 5 所示），在 400~1050 nm 波长范围内其表面平均反射率为 10% 。 The microstructure of the polycrystalline silicon solar cell prepared in this embodiment has a microstructure of 150 to 300 nm (see FIG. 5). The average surface reflectance is 10% in the wavelength range of 400~1050 nm.
实施例三中多晶硅绒面与对比例一中常规酸腐蚀制备的多晶硅绒面的反射光谱对比图参见 图 6 所示。 A comparison of the reflection spectra of the polycrystalline silicon suede prepared by conventional acid etching in the third embodiment and the conventional acid etching in Comparative Example 1 is shown in Fig. 6.
实施例四 Embodiment 4
一种多晶硅太阳电池的绒面结构的制备方法，包括如下步骤： A method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
(1) 将厚度为 180±10μm ，大小为 156mm ×156mm 的 P 型多晶硅片损伤层去除并清洗干净后， 腐蚀制绒，形成微米级绒面； (1) P with a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm After the damaged layer of the polycrystalline silicon wafer is removed and cleaned, the fleece is corroded to form a micron-sized suede;
然后投入到浓度为 0.008mol/L 的 AgNO3 溶液中，于 20 ℃ 条件下反应 120s ；Then, it was put into AgNO 3 solution with a concentration of 0.008 mol/L and reacted at 20 °C for 120 s.
（ 2 ）将上步完成后的硅片放入 HF 与 H2O2 的混合溶液中，其浓度分别为 3mol/L ， 0.1mol/L ，于 20 ℃ 条件下反应 600s ；(2) The silicon wafer after the completion of the above step is placed in a mixed solution of HF and H 2 O 2 at a concentration of 3 mol/L and 0.1 mol/L, respectively, and reacted at 20 ° C for 600 s;
（ 3 ）将上步完成后的硅片放入质量百分比为 69% 硝酸溶液中清洗 300s ，清洗温度为 20 ℃ ； (3) The silicon wafer after the completion of the above step is placed in a mass percentage of 69% nitric acid solution for 300 s, and the cleaning temperature is 20 °C. ;
（ 4 ）将上步完成后的硅片放入质量百分比为 5% 氢氟溶液中清洗 200s ，清洗温度为 20 ℃ ； (4) The silicon wafer after the completion of the previous step is placed in a mass percentage of 5% hydrofluoric solution for 200 s, and the cleaning temperature is 20 °C. ;
（ 5 ）将上步完成后的硅片放入 0.025mol/L 的 TMAH 溶液中，于 20 ℃ 条件下反应 300s ； (5) Put the silicon wafer after the previous step into 0.025mol/L TMAH solution and react at 20 °C. 300s ;
（ 6 ）将上步完成后的硅片用去离子水冲洗干净并甩干。 (6) Rinse the silicon wafer after the completion of the previous step with deionized water and dry it.
对比例二 Comparative example two
一种多晶硅太阳电池的绒面结构的制备方法，包括如下步骤： A method for preparing a suede structure of a polycrystalline silicon solar cell comprises the following steps:
(1) 将厚度为 180±10μm ，大小为 156mm ×156mm 的 P 型多晶硅片损伤层去除并清洗干净后， 腐蚀制绒，形成微米级绒面；然后 投入到浓度为 0.008mol/L 的 AgNO3 溶液中，于 20 ℃ 条件下反应 60 s ；(1) After removing and cleaning the damaged layer of P-type polycrystalline silicon wafer with a thickness of 180±10μm and a size of 156mm × 156mm, the corrugated layer is corroded to form micron-sized suede; then it is put into AgNO 3 with a concentration of 0.008 mol/L. In the solution, the reaction was carried out at 20 ° C for 60 s;
(2) 将上步完成后的硅片放入 HF 与 H2O2 的混合溶液中，其浓度分别为 3mol/L ， 0.1mol/L ，于 20 ℃ 条件下反应 300 s ；(2) The silicon wafer after the completion of the above step is placed in a mixed solution of HF and H 2 O 2 at a concentration of 3 mol/L and 0.1 mol/L, respectively, and reacted at 20 ° C for 300 s;
(3) 将上步完成后的硅片放入质量百分比为 69% 硝酸溶液中清洗 300 s ，清洗温度为 20 ℃ ； (3) The silicon wafer after the previous step is placed in a 69% nitric acid solution for 300 s, and the cleaning temperature is 20 °C. ;
(4) 将上步完成后的硅片放入质量百分比为 5% 氢氟溶液中清洗 200 s ，清洗温度为 20 ℃ ； (4) Put the silicon wafer after the previous step into a 5% hydrogen fluoride solution for 200 s and the cleaning temperature is 20 °C. ;
(5) 清洗、甩干，即可得到所述 多晶硅 太阳能电池的绒面结构。 (5) The suede structure of the polycrystalline silicon solar cell can be obtained by washing and drying.
实施例四中，经过 NaOH 溶液修正刻蚀后的多晶硅太阳电池的绒面结构的尺寸在 150~300nm 之间（见图 7 、 8 所示），在 400~1050nm 波长范围内其表面平均反射率为 15.6% （见图 9 所示）。 In the fourth embodiment, the size of the suede structure of the polycrystalline silicon solar cell after the NaOH solution is etched is 150~300 nm. Between (see Figures 7 and 8), the average surface reflectance is 15.6% in the wavelength range of 400~1050nm (see Figure 9).
对比例二中未进行修正刻蚀而制得的纳米绒面结构为纳米深孔状结构，孔径只有 50nm 左右（见图 10 、 11 所示），在 400~1050nm 波长范围内其表面平均反射率为 5.9% （见图 9 所示）。所述未进行修正刻蚀是如 中国发明专利申请 CN102610692A 公开的方法，其制得的纳米 - 微米复合绒面结构没有上述 步骤 (5) 的修正刻蚀。 The nano-sue structure obtained by the modified etching in Comparative Example 2 is a nano-deep-hole structure with a pore size of only about 50 nm (see Figure 10, 11 shows that the average surface reflectance is 5.9% in the wavelength range of 400~1050nm (see Figure 9). The unmodified etching is as in Chinese invention patent application CN102610692A The disclosed method of producing a nano-micron composite suede structure without the modified etching of step (5) above.
实施例五 Embodiment 5
一种单晶硅太阳电池纳米绒面制备方法，包括如下步骤： A method for preparing a nano-sue surface of a single crystal silicon solar cell, comprising the following steps:
（ 1 ）将厚度为 180±10μm ，大小为 156mm ×156mm 的 P 型单晶硅片损伤层去除并清洗干净后， 腐蚀制绒，形成微米级绒面；然后 投入到浓度为 0.008mol/L 的 AgNO3 溶液中，于 20 ℃ 条件下反应 120 s ；(1) After removing and cleaning the damaged layer of P-type single crystal silicon wafer with a thickness of 180±10 μm and a size of 156 mm × 156 mm, the corrugated layer is corroded to form a micron-sized suede; and then the concentration is 0.008 mol/L. In AgNO 3 solution, the reaction was carried out at 20 °C for 120 s;
（ 2 ）将上步完成后的硅片放入 HF 与 H2O2 的混合溶液中，其浓度分别为 3mol/L,0.1mol/L, 与 20 ℃ 条件下反应 600s ；(2) The silicon wafer after the completion of the above step is placed in a mixed solution of HF and H 2 O 2 at a concentration of 3 mol/L, 0.1 mol/L, and reacted at 20 ° C for 600 s;
（ 3 ）将上步完成后的硅片放入质量百分比为 69% 硝酸溶液中清洗 300s ，清洗温度为 20 ℃ ； (3) The silicon wafer after the completion of the above step is placed in a mass percentage of 69% nitric acid solution for 300 s, and the cleaning temperature is 20 °C. ;
（ 4 ）将上步完成后的硅片放入质量百分比为 5% 氢氟溶液中清洗 200s ，清洗温度为 20 ℃ ； (4) The silicon wafer after the completion of the previous step is placed in a mass percentage of 5% hydrofluoric solution for 200 s, and the cleaning temperature is 20 °C. ;
（ 5 ）将上步完成后的硅片放入 0.025mol/L 的 TMAH 溶液中，与 20 ℃ 条件下反应 300s ； (5) Put the silicon wafer after the previous step into 0.025mol/L TMAH solution and react at 20 °C. 300s ;
（ 6 ）将上步完成后的硅片用去离子水冲洗干净并甩干。 (6) Rinse the silicon wafer after the completion of the previous step with deionized water and dry it.
对比例三 Comparative example three
一种单晶硅太阳电池的绒面结构的制备方法，包括如下步骤： A method for preparing a suede structure of a single crystal silicon solar cell, comprising the following steps:
（ 1 ）将厚度为 180±10μm ，大小为 156mm ×156mm 的 P 型单晶硅片损伤层去除并清洗干净后， 腐蚀制绒，形成微米级绒面；然后 投入到浓度为 0.008mol/L 的 AgNO3 溶液中，于 20 ℃ 条件下反应 120 s ；(1) After removing and cleaning the damaged layer of P-type single crystal silicon wafer with a thickness of 180±10 μm and a size of 156 mm × 156 mm, the corrugated layer is corroded to form a micron-sized suede; and then the concentration is 0.008 mol/L. In AgNO 3 solution, the reaction was carried out at 20 °C for 120 s;
（ 2 ）将上步完成后的硅片放入 HF 与 H2O2 的混合溶液中，其浓度分别为 3mol/L,0.1mol/L, 与 20 ℃ 条件下反应 600s ；(2) The silicon wafer after the completion of the above step is placed in a mixed solution of HF and H 2 O 2 at a concentration of 3 mol/L, 0.1 mol/L, and reacted at 20 ° C for 600 s;
（ 3 ）将上步完成后的硅片放入质量百分比为 69% 硝酸溶液中清洗 300s ，清洗温度为 20 ℃ ； (3) The silicon wafer after the completion of the above step is placed in a mass percentage of 69% nitric acid solution for 300 s, and the cleaning temperature is 20 °C. ;
（ 4 ）将上步完成后的硅片放入质量百分比为 5% 氢氟溶液中清洗 200s ，清洗温度为 20 ℃ ； (4) The silicon wafer after the completion of the previous step is placed in a mass percentage of 5% hydrofluoric solution for 200 s, and the cleaning temperature is 20 °C. ;
（ 5 ）清洗、甩干，即可得到所述 单晶硅 太阳能电池的绒面结构。 (5) The suede structure of the single crystal silicon solar cell can be obtained by washing and drying.
实施例五中，经过 NaOH 溶液修正刻蚀后的单晶硅太阳电池的绒面结构的尺寸在 150~300nm 之间（见图 12 、 13 所示），在 400~1050nm 波长范围内其表面平均反射率为 6.4% （见图 14 所示）。 In the fifth embodiment, the size of the suede structure of the single crystal silicon solar cell after being etched by the NaOH solution is 150 to 300 nm. Between (see Figures 12 and 13), the average surface reflectance is 6.4% in the wavelength range of 400~1050nm (see Figure 14).
对比例三中未进行修正刻蚀而制得的纳米绒面结构为纳米深孔状结构，孔径只有 50nm 左右（见图 15 、 16 所示），在 400~1050nm 波长范围内其表面平均反射率为 5.0% （见图 14 所示）。所述未进行修正刻蚀是如中国发明专利申请 CN102610692A 公开的方法，其制得的纳米 - 微米复合绒面结构没有上述 步骤 (5) 的修正刻蚀。 The nano-sue structure obtained by the modified etching in Comparative Example 3 is a nano-deep-hole structure with a pore size of only about 50 nm (see Figure 15 16) shows an average surface reflectance of 5.0% in the wavelength range of 400 to 1050 nm (see Figure 14). The unmodified etching is as in Chinese invention patent application CN102610692A The disclosed method of producing a nano-micron composite suede structure without the modified etching of step (5) above.

Claims (7)

1 ．一种 晶体硅太阳能电池 的绒面结构的制备方法，其特征在于，包括如下步骤： 1 . A method for preparing a suede structure of a crystalline silicon solar cell, comprising the steps of:
(1) 将多晶硅硅片进行清洗、腐蚀制绒，形成微米级绒面；(1) cleaning and etching the polycrystalline silicon wafer to form micron-sized suede;
(2) 将上述硅片放入含有金属离子的溶液中浸泡，使硅片表面涂覆一层金属纳米颗粒；(2) immersing the above silicon wafer in a solution containing metal ions to coat a surface of the silicon wafer with a layer of metal nanoparticles;
所述金属离子选自金离子、银离子和铜离子中的一种；The metal ion is selected from one of a gold ion, a silver ion, and a copper ion;
(3) 用第一化学腐蚀液腐蚀硅片表面，形成纳米级绒面；(3) etching the surface of the silicon wafer with a first chemical etching solution to form a nano-scale suede;
所述第一化学腐蚀液选自以下混合溶液中的一种： HF 与 H2O2 的混合溶液、 HF 与 HNO3 的混合溶液、 HF 与 H2CrO4 的混合溶液；The first chemical etching solution is selected from one of the following mixed solutions: a mixed solution of HF and H 2 O 2 , a mixed solution of HF and HNO 3 , a mixed solution of HF and H 2 CrO 4 ;
其中， HF 的浓度为 1~15 mol/L ， H2O2 、 HNO3 或 H2CrO4 的浓度为 0.05~0.5 mol/L ；The concentration of HF is 1~15 mol/L, and the concentration of H 2 O 2 , HNO 3 or H 2 CrO 4 is 0.05~0.5 mol/L;
(4) 分别用第一清洗液、第二清洗液、去离子水清洗上述硅片，去除金属颗粒；(4) cleaning the silicon wafer with the first cleaning solution, the second cleaning solution, and deionized water, respectively, to remove the metal particles;
所述第一清洗液 为质量百分比为 27~69% 的硝酸溶液，清洗时间为 60~1200 秒，清洗温度为 5~85℃ ；The first cleaning solution is a nitric acid solution having a mass percentage of 27 to 69%, the cleaning time is 60 to 1200 seconds, and the cleaning temperature is 5 to 85 ° C. ;
所述第二清洗液 为质量百分比为 1~10% 的氢氟酸溶液，清洗时间为 60~600 秒，清洗温度为 5~45℃ ；The second cleaning solution is a hydrofluoric acid solution having a mass percentage of 1 to 10%, the cleaning time is 60 to 600 seconds, and the cleaning temperature is 5 to 45 ° C. ;
(5) 将上述硅片放入第二化学腐蚀液中 进行微结构修正刻蚀；(5) placing the above silicon wafer into the second chemical etching solution for microstructure modification etching;
所述 第二化学腐蚀液选自以下溶液中的一种： NaOH 溶液、 KOH 溶液、四甲基氢氧化铵溶液、 HNO3 与 HF 酸的混合溶液；The second chemical etching solution is selected from one of the following solutions: a NaOH solution, a KOH solution, a tetramethylammonium hydroxide solution, a mixed solution of HNO 3 and HF acid;
当选自 NaOH 溶液时，其浓度为 0.001~0.1 mol/L ，反应时间为 10~1000 秒，反应温度为 5~85℃；When selected from NaOH solution, the concentration is 0.001~0.1 mol/L, the reaction time is 10~1000 seconds, and the reaction temperature is 5~85°C;
当选自 KOH 溶液时，其浓度为 0.001~0.1 mol/L ，反应时间为 10~1000 秒，反应温度为 5~85℃；When selected from KOH solution, the concentration is 0.001~0.1 mol/L, the reaction time is 10~1000 seconds, and the reaction temperature is 5~85°C;
当选自四甲基氢氧化铵溶液时，其浓度为 0.001~0.1 mol/L ，反应时间为 10~1000 秒，反应温度为 5~85℃；When selected from tetramethylammonium hydroxide solution, the concentration is 0.001~0.1 mol/L, the reaction time is 10~1000 seconds, and the reaction temperature is 5~85°C;
当选自 HNO3 与 HF 酸的混合溶液时， HF 与 HNO3 的浓度分别为 0.05~0.5 mol/L 、 1~10 mol/L ，反应时间为 10~1000 秒，反应温度为 5~45℃；When selected from a mixed solution of HNO 3 and HF acid, the concentrations of HF and HNO 3 are 0.05~0.5 mol/L and 1~10 mol/L, respectively, the reaction time is 10~1000 seconds, and the reaction temperature is 5~45 °C;
(6) 清洗、甩干，即可得到所述 晶体硅太阳能电池 的绒面结构。(6) The suede structure of the crystalline silicon solar cell can be obtained by washing and drying.
2 ．根据权利要求 1 所述的制备方法 ， 其特征在于：所述步骤 (2) 中的纳米级金属颗粒的浓度为 0.0001~0.1 mol/L 。2 . The preparation method according to claim 1, wherein the concentration of the nano-sized metal particles in the step (2) is 0.0001 to 0.1. Mol/L.
3 ．根据权利要求 1 所述的制备方法 ， 其特征在于：所述步骤 (2) 中，浸泡时间为 10~1000 秒，溶液温度为 5~85℃ 。3 . The preparation method according to claim 1, wherein in the step (2), the immersion time is 10 to 1000 seconds, and the solution temperature is 5~85°C.
4 ．根据权利要求 1 所述的制备方法 ， 其特征在于：所述步骤 (3) 的腐蚀时间为 30~3000 秒，反应温度为 5~45℃。4 . The preparation method according to claim 1, wherein the etching time of the step (3) is 30 to 3000 seconds, and the reaction temperature is 5~45°C.
5 ．根据权利要求 1 所述的制备方法得到的 晶体硅太阳能电池 的绒面结构。5 . A pile structure of a crystalline silicon solar cell obtained by the production method according to claim 1.
6 ．根据权利要求 5 所述的 晶体硅太阳能电池 的绒面结构 ， 其特征在于：所述 晶体硅太阳能电池为多晶硅太阳能电池，其 绒面结构的反射率为 12%~20% 。6 . The suede structure of a crystalline silicon solar cell according to claim 5, wherein the crystalline silicon solar cell is a polycrystalline silicon solar cell, The reflectivity of the suede structure is 12% to 20%.
7 ．根据权利要求 5 所述的 晶体硅太阳能电池 的绒面结构 ， 其特征在于：所述 晶体硅太阳能电池为单晶硅太阳能电池，其 绒面结构的反射率为 5%~15% 。7 . The suede structure of a crystalline silicon solar cell according to claim 5, wherein the crystalline silicon solar cell is a monocrystalline silicon solar cell, The reflectivity of the suede structure is 5%~15%.
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CN105140343B (en) * 2015-08-31 2018-02-13 南京航空航天大学 A kind of black silicon structure of polycrystalline and its liquid phase preparation process
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EP4290590A1 (en) 2022-06-10 2023-12-13 Zhejiang Jinko Solar Co., Ltd. Solar cell

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110070744A1 (en) * 2009-09-18 2011-03-24 Zhi-Wen Sun Silicon Texturing Formulations for Solar Applications
CN102034900A (en) * 2010-10-27 2011-04-27 晶澳太阳能有限公司 Texture etching method for quasi-monocrystalline silicon wafer
CN102610692A (en) * 2012-03-09 2012-07-25 润峰电力有限公司 Method for preparing crystalline silicon nanometer and micrometer composite texture surface
CN102618937A (en) * 2012-04-10 2012-08-01 苏州阿特斯阳光电力科技有限公司 Texture etching technology of single crystalline silicon solar cell
CN103219428A (en) * 2013-04-12 2013-07-24 苏州大学 Textured structure of crystalline silicon solar cell and preparation method thereof

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4049329B2 (en) * 2002-06-06 2008-02-20 関西ティー・エル・オー株式会社 Method for producing polycrystalline silicon substrate for solar cell
JP3925867B2 (en) * 2003-12-17 2007-06-06 関西ティー・エル・オー株式会社 Method for manufacturing a silicon substrate with a porous layer
TWI244135B (en) * 2004-12-31 2005-11-21 Ind Tech Res Inst Method of making solar cell
JP2007194485A (en) * 2006-01-20 2007-08-02 Osaka Univ Manufacturing method of silicon substrate for solar battery
US8178419B2 (en) * 2008-02-05 2012-05-15 Twin Creeks Technologies, Inc. Method to texture a lamina surface within a photovoltaic cell
CN101752450B (en) * 2008-12-08 2012-02-08 湖南天利恩泽太阳能科技有限公司 Multiplex velvet making method for crystalline silicon solar battery slice
CN101661972B (en) * 2009-09-28 2011-07-20 浙江大学 Process for manufacturing monocrystalline silicon solar cell texture with low surface reflectivity
JP2010245568A (en) * 2010-07-21 2010-10-28 Mitsubishi Electric Corp Method of manufacturing solar cell
CN102130205A (en) * 2010-12-10 2011-07-20 上海太阳能电池研究与发展中心 Method for performing surface catalytic texturing on polycrystalline silicon solar cell
WO2012157179A1 (en) * 2011-05-17 2012-11-22 株式会社Sumco Method for manufacturing wafer for solar cell, method for manufacturing solar cell, and method for manufacturing solar cell module
JP5467697B2 (en) * 2011-10-07 2014-04-09 株式会社ジェイ・イー・ティ Manufacturing method of solar cell
CN102544199A (en) * 2011-12-15 2012-07-04 浙江鸿禧光伏科技股份有限公司 Method for acid-etching honeycomb structure of crystalline silicon cell
CN102703989B (en) * 2012-05-28 2015-12-02 天威新能源控股有限公司 Class monocrystalline solar cells leather producing process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110070744A1 (en) * 2009-09-18 2011-03-24 Zhi-Wen Sun Silicon Texturing Formulations for Solar Applications
CN102034900A (en) * 2010-10-27 2011-04-27 晶澳太阳能有限公司 Texture etching method for quasi-monocrystalline silicon wafer
CN102610692A (en) * 2012-03-09 2012-07-25 润峰电力有限公司 Method for preparing crystalline silicon nanometer and micrometer composite texture surface
CN102618937A (en) * 2012-04-10 2012-08-01 苏州阿特斯阳光电力科技有限公司 Texture etching technology of single crystalline silicon solar cell
CN103219428A (en) * 2013-04-12 2013-07-24 苏州大学 Textured structure of crystalline silicon solar cell and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
K. TSUJINO ET AL.: "Texturization of Multicrystalline Silicon Wafers for Solar Cells by Chemical Treatment Using Metallic Catalyst.", SOLAR ENERGY MATERIALS & SOLAR CELLS., vol. 90, no. 1, 19 August 2005 (2005-08-19), pages 100 - 110 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105206709A (en) * 2015-10-10 2015-12-30 浙江晶科能源有限公司 Treatment method used for optimizing black silicon surface structure
WO2017221710A1 (en) * 2016-06-20 2017-12-28 株式会社ジェイ・イー・ティ Solar cell manufacturing method
WO2018189131A1 (en) 2017-04-13 2018-10-18 Rct Solutions Gmbh Device and method for chemically treating a semiconductor substrate having a sawn surface structure
DE102017206432A1 (en) 2017-04-13 2018-10-18 Rct Solutions Gmbh Apparatus and method for chemically treating a semiconductor substrate having a sawn surface structure
CN111769175B (en) * 2019-03-15 2022-08-26 中国科学院物理研究所 PERC single crystalline silicon solar cell and preparation method thereof
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CN111128714B (en) * 2019-12-31 2022-06-03 杭州中欣晶圆半导体股份有限公司 Acid etching process for reducing heavily boron-doped color spots
CN111128714A (en) * 2019-12-31 2020-05-08 杭州中欣晶圆半导体股份有限公司 Acid etching process for reducing heavily boron-doped color spots
CN112466995A (en) * 2020-11-23 2021-03-09 宁波尤利卡太阳能股份有限公司 Monocrystalline texturing method of PERC battery
CN112885928A (en) * 2021-03-30 2021-06-01 东南大学 Method for quickly forming octagonal pyramid structure on silicon wafer
CN112885928B (en) * 2021-03-30 2022-11-15 东南大学 Method for quickly forming octagonal pyramid structure on silicon wafer
CN113937172A (en) * 2021-10-19 2022-01-14 温州大学 Novel composite suede structure preparation method of crystalline silicon solar cell
CN113937172B (en) * 2021-10-19 2023-10-10 温州大学 Preparation method of novel composite suede structure of crystalline silicon solar cell
CN114551644A (en) * 2022-02-22 2022-05-27 江西中弘晶能科技有限公司 Design of surface micron-nano composite structure for improving conversion efficiency of high-efficiency battery piece
CN115117202A (en) * 2022-07-05 2022-09-27 晶澳（扬州）太阳能科技有限公司 Preparation method of solar cell and solar cell
CN115161032A (en) * 2022-07-05 2022-10-11 北京师范大学 Etching solution and method suitable for monocrystalline silicon wafer
CN116004233A (en) * 2022-12-12 2023-04-25 嘉兴市小辰光伏科技有限公司 Etching additive for improving uniformity of textured surface of silicon wafer and use method

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