WO2015032154A1 - 多晶硅片制绒添加剂及其使用方法 - Google Patents

多晶硅片制绒添加剂及其使用方法 Download PDF

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Publication number
WO2015032154A1
WO2015032154A1 PCT/CN2013/089693 CN2013089693W WO2015032154A1 WO 2015032154 A1 WO2015032154 A1 WO 2015032154A1 CN 2013089693 W CN2013089693 W CN 2013089693W WO 2015032154 A1 WO2015032154 A1 WO 2015032154A1
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Prior art keywords
texturing
polycrystalline silicon
silicon wafer
additive
texturizing
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PCT/CN2013/089693
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English (en)
French (fr)
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符黎明
章圆圆
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常州时创能源科技有限公司
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Priority to SG11201405972TA priority Critical patent/SG11201405972TA/en
Priority to JP2016539393A priority patent/JP2016531835A/ja
Priority to LTEP13893094.6T priority patent/LT2891733T/lt
Priority to ES13893094.6T priority patent/ES2591133T3/es
Priority to EP13893094.6A priority patent/EP2891733B1/en
Priority to KR1020147030500A priority patent/KR101687767B1/ko
Priority to US14/376,502 priority patent/US9935233B2/en
Publication of WO2015032154A1 publication Critical patent/WO2015032154A1/zh

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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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
    • Y02E10/546—Polycrystalline silicon PV cells
    • 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
    • Y02E10/547—Monocrystalline silicon PV cells

Definitions

  • the present invention relates to polycrystalline sheet fluffing additives and methods of use thereof. Background technique
  • the surface of the silicon wafer is the key link.
  • the effect of the cashmere directly affects the conversion efficiency and yield of the final cell.
  • the polycrystalline silicon wafer is composed of crystal grains of different crystal orientations, and the crystal orientation of each crystal grain is randomly distributed
  • the surface of the polycrystalline silicon wafer is subjected to texturing by a wet chemical etching method using an acidic solution in a general texturing process.
  • the texturing process is based on the principle of isotropic corrosion of silicon by an acidic solution, forming similar pit-like suede on different grain surfaces of the silicon wafer, and the morphology and grain orientation of the suede are not present, and are commonly used in industrial production.
  • the acid solution is composed of nitric acid, hydrofluoric acid, deionized water, and the like.
  • the texturing effect of this acid solution is not very satisfactory, and the problems include: large size and uniformity of the suede surface, and the chromatic aberration between different grains is relatively obvious, and there are macroscopic features such as black line-like etch pits.
  • the surface reflectance is high and the texturing stability is not good. Therefore, if the above problem can be solved by adding a texturing additive to an acid solution, it will be of great significance. Summary of the invention
  • the object of the present invention is to provide a polysilicon sheet velvet additive and a method for using the same, and the polysilicon sheet velvet additive is applied to the suede production of a polycrystalline silicon sheet, and a micro-hole type with good uniformity and no chromatic aberration between crystal grains can be obtained.
  • Micro-structured suede thereby reducing the reflectivity and effectively reducing the amount of black line generation;
  • the polysilicon sheeting additive changes the reaction mechanism, controls the reaction speed, enables the texturing to be carried out under conditions close to room temperature, and greatly reduces the temperature control cost; It can effectively remove the roller print, make the silicon wafer cleaner, and match the subsequent process, and the battery performance is more stable.
  • the present invention provides a polycrystalline silicon sheet texturing additive comprising the components comprising: triamine citrate, polyvinylpyrrolidone, polyvinyl alcohol, citric acid and the balance of water.
  • the mass percentage of each component in the polycrystalline silicon fluffing additive is: citric acid triamine 0.2% ⁇ 0.5%, polyvinylpyrrolidone 0.1% ⁇ 1%, polyvinyl alcohol 0.1% ⁇ 0.2%, lemon Acid 2% ⁇ 2.5%, the balance is water.
  • the water is deionized water.
  • the invention also provides a cashmere liquid for the fluffing of a polycrystalline silicon sheet, which comprises an acid solution and the above-mentioned polycrystalline silicon sheet fluffing additive, wherein the mass ratio of the polycrystalline silicon flake additive to the acid solution is 0.1 to 0.6:100;
  • the acid solution is formulated with 7% to 14% aqueous HF solution and 25% to 50% aqueous HN0 3 solution; the HF aqueous solution contains 49% HF, and the HNO 3 aqueous solution contains 69% HN0 3 ; Wherein the percentage is a mass percentage.
  • the present invention also provides a method of texturing a polycrystalline silicon sheet, wherein the polycrystalline silicon wafer is surface-textured by the above-described texturing liquid.
  • the surface texturing has a texturing temperature of 5 to 25 ° C and a texturing time of 45 to 180 s.
  • the specific steps of the method for forming the above polycrystalline silicon sheet include:
  • the texturing additive 0.2% to 0.5% by weight of triamine citrate, 0.1% to 1% of polyvinylpyrrolidone, 0.1% to 0.2% of polyvinyl alcohol, 2% to 2.5% of citric acid Adding to the balance of water, mixing and uniformly forming into a texturing additive; wherein the water is preferably deionized water;
  • the polycrystalline silicon sheet is immersed in the fluffing liquid prepared in the step 2) to perform surface texturing, the texturing temperature is 5 to 25 ° C, and the texturing time is 45 to 180 s.
  • the invention has the advantages and beneficial effects of providing a polycrystalline silicon sheet fluffing additive and a using method thereof, wherein the polycrystalline silicon sheet fluffing additive is applied to the suede production of the polycrystalline silicon sheet, and the uniformity is good, and the crystal grains have no obvious chromatic aberration.
  • micro-cavity micro-structured suede thereby reducing the reflectivity and effectively reducing the amount of black line generation;
  • the polycrystalline wafer fluffing additive changes the reaction mechanism, controls the reaction speed, and enables the texturing to be carried out under conditions close to room temperature, greatly reducing the temperature Control the cost; It can also effectively remove the roller print, make the silicon wafer cleaner, match the subsequent process, and the battery performance is more stable.
  • Figure 1 is a scanning electron micrograph of a surface of a polycrystalline silicon wafer in accordance with a third embodiment of the present invention. detailed description
  • a method for softening a polycrystalline silicon sheet taking the following process steps:
  • a texturing additive 0.2 g of citric acid triamine, 0.1 g of polyvinylpyrrolidone, 0.1 g of polyvinyl alcohol, and 2 g of citric acid are dissolved in deionized water to obtain 100 g of a texturing additive;
  • Texturing The polycrystalline silicon cell is immersed in the fluffing liquid for surface flocking, the texturing temperature is 5 °C, and the texturing time is 180 s.
  • a method for softening a polycrystalline silicon sheet taking the following process steps:
  • Texturing The polycrystalline silicon battery is immersed in the fluffing liquid for surface texturing, the texturing temperature is 25 ° C, and the texturing time is 45 s.
  • a method for softening a polycrystalline silicon sheet taking the following process steps:
  • a texturing additive 1.2 g of citric acid triamine, 1.5 g of polyvinylpyrrolidone, 0.45 g of polyvinyl alcohol, and 6.9 g of citric acid are dissolved in deionized water using deionized water as a solvent to obtain 300 g of a texturing additive;
  • Texturing The polycrystalline silicon battery sheet is immersed in the fluffing liquid for surface texturing, the texturing temperature is 12 ° C, and the texturing time is 100 s.
  • Fig. 1 is a scanning electron microscope plane photograph of the surface of the polycrystalline silicon sheet obtained in the third embodiment. It can be seen from the figure that a micro-cavity microstructured suede is formed on the surface of the polycrystalline silicon sheet after the texturing, and the suede distribution is compared. Evenly.
  • the above description is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make several improvements and retouchings without departing from the technical principles of the present invention. It should also be considered as the scope of protection of the present invention.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Computer Hardware Design (AREA)
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Abstract

本发明提供一种多晶硅片制绒添加剂。本发明还提供一种用于多晶硅片制绒的制绒液，其含有酸溶液和上述多晶硅片制绒添加剂。本发明还提供一种多晶硅片的制绒方法，利用上述制绒液对多晶硅片进行表面制绒。该多晶硅片制绒添加剂应用于多晶硅片的绒面制作，可以得到均匀性好、晶粒间无明显色差的微洞型的微结构绒面，从而降低反射率，有效减少黑线产生数量；该多晶硅片制绒添加剂改变反应机理，控制反应速度，使制绒可以在接近室温的条件下进行，大大降低温度控制成本；还能有效去除滚轮印，使硅片更清洁，与后道工艺更匹配，电池性能更稳定。

Description

多晶硅片制绒添加剂及其使用方法 技术领域
本发明涉及多晶硅片制绒添加剂及其使用方法。 背景技术
在多晶硅太阳电池制造过程中， 硅片表面制绒是关键的环节。 制 绒的效果直接影响了最终电池片的转换效率和成品率。由于多晶硅片 由不同晶向的晶粒组成， 并且各个晶粒的晶向随意分布， 因此， 在一 般制绒工艺中多釆用酸性溶液的湿化学腐蚀方法对多晶硅片表面进 行制绒。 该制绒工艺基于酸性溶液对硅的各向同性腐蚀原理， 在硅片 不同晶粒表面形成相似的凹坑状绒面， 绒面的形貌与晶粒取向性无 目前， 工业生产中常用的酸溶液由硝酸、 氢氟酸和去离子水等组 成。 这种酸溶液的制绒效果并不是十分理想， 存在的问题包括： 绒面 尺寸较大且均匀性不佳， 不同晶粒之间色差比较明显， 存在宏观形貌 如黑线状的深腐蚀坑， 表面反射率较高， 制绒稳定性不好。 因此， 如 果可以通过在酸溶液中加入制绒添加剂， 来解决上述问题， 将具有重 要的意义。 发明内容
本发明的目的在于提供一种多晶硅片制绒添加剂及其使用方法， 该多晶硅片制绒添加剂应用于多晶硅片的绒面制作，可以得到均匀性 好、 晶粒间无明显色差的微洞型的微结构绒面， 从而降低反射率， 有 效减少黑线产生数量； 该多晶硅片制绒添加剂改变反应机理， 控制反 应速度， 使制绒可以在接近室温的条件下进行， 大大降低温度控制成 本； 还能有效去除滚轮印， 使硅片更清洁， 与后道工艺更匹配， 电池 性能更稳定。 为实现上述目的， 本发明提供一种多晶硅片制绒添加剂， 其组分 包括： 柠檬酸三胺、聚乙烯吡咯烷酮、聚乙烯醇、柠檬酸和余量的水。
优选的， 所述多晶硅片制绒添加剂中各组分的质量百分含量为： 柠檬酸三胺 0.2% ~ 0.5%, 聚乙烯吡咯烷酮 0.1%~1%, 聚乙烯醇 0.1% ~ 0.2%, 柠檬酸 2% ~ 2.5%, 余量为水。
优选的， 所述水为去离子水。
本发明还提供一种用于多晶硅片制绒的制绒液，其含有酸溶液和 上述多晶硅片制绒添加剂，所述多晶硅片制绒添加剂与酸溶液的质量 比为 0.1 ~ 0.6: 100;所述酸溶液中配入了 7%~ 14%的 HF水溶液和 25%~ 50%的 HN03水溶液； 所述 HF水溶液中含有 49%的 HF, 所述 HN03水溶液中 含有 69%的 HN03;其中， 所述百分比为质量百分比。
本发明还提供一种多晶硅片的制绒方法，利用上述制绒液对多晶 硅片进行表面制绒。
优选的， 所述表面制绒的制绒温度为 5 ~25°C, 制绒时间为 45 ~ 180s。
上述多晶硅片的制绒方法的具体步骤包括：
1 )配置制绒添加剂： 将质量百分比为 0.2% ~ 0.5%的柠檬酸三胺、 0.1%~1%的聚乙烯吡咯烷酮、 0.1%~0.2%的聚乙烯醇、 2% ~ 2.5%的柠 檬酸加入到余量的水中， 混合均匀配成制绒添加剂； 其中水优选为去 离子水；
2)配置制绒液： 将步骤 1 )制成的制绒添加剂加到酸溶液中， 混 合均匀配成制绒液； 所述制绒添加剂与酸溶液的质量比为 0.1 ~
0.6: 100; 所述酸溶液中配入了 7%~ 14%的 HF水溶液和 25%~ 50%的 HN03 水溶液； 所述 HF水溶液中含有 49%的 HF, 所述 HN03水溶液中含有 69%的 HN03;其中， 所述百分比为质量百分比；
3)将多晶硅片浸入步骤 2 )制得的制绒液中进行表面制绒， 制绒 温度为 5~25°C, 制绒时间为 45 ~180s。 本发明的优点和有益效果在于：提供一种多晶硅片制绒添加剂及 其使用方法， 该多晶硅片制绒添加剂应用于多晶硅片的绒面制作， 可 以得到均匀性好、 晶粒间无明显色差的微洞型的微结构绒面， 从而降 低反射率， 有效减少黑线产生数量； 该多晶硅片制绒添加剂改变反应 机理， 控制反应速度， 使制绒可以在接近室温的条件下进行， 大大降 低温度控制成本； 还能有效去除滚轮印， 使硅片更清洁， 与后道工艺 更匹配， 电池性能更稳定。 附图说明
图 1是本发明实施例 3的多晶硅片表面绒面的扫描电镜平面图。 具体实施方式
下面结合附图和实施例， 对本发明的具体实施方式作进一步描 述。 以下实施例仅用于更加清楚地说明本发明的技术方案， 而不能以 此来限制本发明的保护范围。
本发明具体实施的技术方案是：
实施例 1
一种多晶硅片的制绒方法， 釆取如下工艺步骤：
1 )配制制绒添加剂: 将 0. 2g柠檬酸三胺、 0. l g聚乙烯吡咯烷酮、 0. l g聚乙烯醇、 2 g柠檬酸溶解于去离子水中， 得到 100g制绒添加剂；
2 ) 配置制绒液： 将 7kg的 HF水溶液（HF水溶液中 HF的质量百分含
69%)溶于去离子水中， 得到 100kg酸溶液； 然后在该酸溶液中加入步 骤 1 ) 制成的 100g制绒添加剂得到制绒液；
3 )制绒： 将多晶硅电池片浸入制绒液中进行表面制绒， 制绒温 度为 5 °C , 制绒时间为 180s。
实施例 2
一种多晶硅片的制绒方法， 釆取如下工艺步骤：
1 ) 配制制绒添加剂： 以去离子水为溶剂， 将 3g柠檬酸三胺、 6g 聚乙烯吡咯烷酮、 1.2g聚乙烯醇、 15g柠檬酸溶解于去离子水中， 得 到 600g制绒添加剂；
2 )配置制绒液： 将 14kg的 HF水溶液（HF水溶液中 HF的质量百分含
69%)混合， 得到 100kg的酸溶液； 然后在该酸溶液中加入步骤 1 )制成 的 600g制绒添加剂得到制绒液；
3 )制绒： 将多晶硅电池片浸入制绒液中进行表面制绒， 制绒温 度为 25°C, 制绒时间为 45s。
实施例 3
一种多晶硅片的制绒方法， 釆取如下工艺步骤：
1 ) 配制制绒添加剂： 以去离子水为溶剂， 将 1.2g柠檬酸三胺、 1.5g聚乙烯吡咯烷酮、 0.45g聚乙烯醇、 6.9g柠檬酸溶解于去离子水 中， 得到 300g制绒添加剂；
2 )配置制绒液： 将 10kg的 HF水溶液（HF水溶液中 HF的质量百分含
69%)溶于去离子水中， 得到 100kg的酸溶液； 然后在该酸溶液中加入 步骤 1 )制成的 300g制绒添加剂得到制绒液；
3 )制绒： 将多晶硅电池片浸入制绒液中进行表面制绒， 制绒温 度为 12°C, 制绒时间为 100s。
图 1给出了本实施例 3得到的多晶硅片表面绒面的扫描电镜平面 照片，从图中可以看到制绒后在多晶硅片表面形成了微洞型的微结构 绒面， 绒面分布比较均匀。 以上所述仅是本发明的优选实施方式， 应当指出， 对于本技术领 域的普通技术人员来说， 在不脱离本发明技术原理的前提下， 还可以 做出若干改进和润饰， 这些改进和润饰也应视为本发明的保护范围。

Claims

权 利 要 求 书
1、 多晶硅片制绒添加剂， 其特征在于， 其组分包括： 柠檬酸三 胺、 聚乙烯吡咯烷酮、 聚乙烯醇、 柠檬酸和余量的水。
2、 根据权利要求 1所述的多晶硅片制绒添加剂， 其特征在于， 所 述多晶硅片制绒添加剂中各组分的质量百分含量为： 柠檬酸三胺
0.2% -0.5%, 聚乙烯吡咯烷酮 0.1%~1%, 聚乙烯醇 0.1%~ 0.2%, 柠檬 酸 2%~2.5%, 余量为水。
3、根据权利要求 1或 2所述的多晶硅片制绒添加剂， 其特征在于， 所述水为去离子水。
4、 用于多晶硅片制绒的制绒液， 其特征在于， 其含有酸溶液和 权利要求 1-3中任意一项的多晶硅片制绒添加剂， 所述多晶硅片制绒 添加剂与酸溶液的质量比为 0.1 ~ 0.6: 100;所述酸溶液中配入了 7% ~ 14%的 HF水溶液和 25%~ 50%的 HN03水溶液； 所述 HF水溶液中含有 49%的 HF, 所述 HN03水溶液中含有 69%的 HN03;其中， 所述百分比为质量百分 比。
5、 多晶硅片的制绒方法， 其特征在于， 利用权利要求 4所述的制 绒液对多晶硅片进行表面制绒。
6、 根据权利要求 5所述多晶硅片的制绒方法， 其特征在于， 所述 表面制绒的制绒温度为 5 ~ 25°C , 制绒时间为 45 ~ 180s。
7、 根据权利要求 6所述多晶硅片的制绒方法， 其特征在于， 其具 体步骤包括：
1 )配置制绒添加剂： 将质量百分比为 0.2% ~ 0.5%的柠檬酸三胺、 0.1%~1%的聚乙烯吡咯烷酮、 0.1%~0.2%的聚乙烯醇、 2% ~ 2.5%的柠 檬酸加入到余量的水中， 混合均匀配成制绒添加剂；
2)配置制绒液： 将步骤 1 )制成的制绒添加剂加到酸溶液中， 混 合均匀配成制绒液； 所述制绒添加剂与酸溶液的质量比为 0.1 ~ 0.6: 100; 所述酸溶液中配入了 7%~ 14%的 HF水溶液和 25%~ 50%的 HN03 水溶液； 所述 HF水溶液中含有 49%的 HF, 所述 HN03水溶液中含有 69%的 HN03;其中， 所述百分比为质量百分比；
3)将多晶硅片浸入步骤 2)制得的制绒液中进行表面制绒， 制绒 温度为 5~25°C, 制绒时间为 45~180s。
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