WO2018120433A1 - 一种太阳能电池硅片刻蚀用水膜溶液及其应用 - Google Patents

一种太阳能电池硅片刻蚀用水膜溶液及其应用 Download PDF

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WO2018120433A1
WO2018120433A1 PCT/CN2017/076574 CN2017076574W WO2018120433A1 WO 2018120433 A1 WO2018120433 A1 WO 2018120433A1 CN 2017076574 W CN2017076574 W CN 2017076574W WO 2018120433 A1 WO2018120433 A1 WO 2018120433A1
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water film
etching
silicon wafer
film solution
solar cell
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PCT/CN2017/076574
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English (en)
French (fr)
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孙铁囤
张凯胜
吴家宏
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常州亿晶光电科技有限公司
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Priority to EP17887574.6A priority Critical patent/EP3565008B1/en
Publication of WO2018120433A1 publication Critical patent/WO2018120433A1/zh

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    • 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
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • 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
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • H01L21/3081—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their composition, e.g. multilayer masks, materials
    • 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
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • H01L21/3083—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/3085—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by their behaviour during the process, e.g. soluble masks, redeposited masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—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
    • 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 invention belongs to the technical field of solar cells, and in particular relates to a water film solution for solar cell silicon wafer etching and an application thereof.
  • the general method for manufacturing a silicon solar cell is to first form a clean P-type or N-type silicon wafer through a texturing process to form a suede structure; secondly, diffusion on the surface of the silicon wafer to form an N+ or P+ emitter, after the wet method
  • the diffusion layer on the side and back of the silicon wafer is removed by etching; then a SiN film having anti-reflection function is formed on the front surface thereof; finally, a metal electrode is separately formed on the front and back sides of the silicon wafer, and a crystalline silicon solar cell is formed through a sintering process.
  • the wet etching before the wet etching, it is generally required to use a water film protection method to spray a water film on the front surface of the silicon wafer before the silicon wafer enters the etching groove, thereby preventing the liquid medicine from turning over to the front side of the silicon wafer to cause the engraving.
  • the PN junction of the diffusion surface is destroyed.
  • the problem is that when etching or polishing with a mixed acid, the high-concentration acid (such as HF, nitric acid, etc.) in the etching bath is easily volatilized, and the acid volatilized as the amount of volatilization increases is redissolved in the water film.
  • the present invention is directed to the above technical problem, and provides a solar cell silicon wafer etching water film solution, which is formed by dispersing glucose and difluorosulfonimide salt in water.
  • the content of glucose in the water film solution is 1.5 to 4.0 g/L
  • the bisfluorosulfonimide salt is sodium bisfluorosulfonimide or lithium bisfluorosulfonimide, and its content in the water film solution is 0.1 to 0.35 mol/L.
  • the water film solution can be added to the deionized water and stirred evenly during the preparation process.
  • the invention also provides an application of the above water film solution:
  • the water film is sprayed on the diffusion surface by a water film spray coating technique, and the water film is adsorbed on the surface by hydrophilicity of the silica;
  • the silicon wafer processed in the step (1) is introduced into the etching bath to etch the PN junction on the back side and the edge.
  • the silicon wafer is etched by floating on the etching liquid, or the liquid etching roller is used to bring the etching liquid to the back surface of the silicon wafer for etching.
  • the invention has the beneficial effects that the present invention is found by synergistically adding glucose and a difluorosulfonimide salt in a water film solution, which can suppress the re-dissolution of the volatilized acid in the etching solution in the water film, thereby reducing the pair
  • the diffusion surface (positive surface) of the PSG and PN junction is destroyed, and the water film solution itself has no damage to the diffusion surface and the silicon wafer substrate, and glucose as a natural green additive does not have any pollution itself;
  • the viscosity of the water film containing the additive is slightly larger than the viscosity of the pure water under the same conditions, and the increase of the viscosity promotes the corresponding increase of the surface tension of the edge of the silicon wafer, and can avoid the overetching to some extent during etching;
  • the etching amount of the acid etching in the prior art can only reach 4 to 5 micrometers, increasing the concentration of the etching solution or increasing the etching time causes vapor phase corrosion on the surface of the battery, destroying the surface PN junction, and 4 to 5 micrometers.
  • the etching amount is difficult to completely remove the suede forming polishing structure for some silicon wafers having a suede structure on the back surface, which is particularly obvious for the back passivation battery, which causes the polishing surface to be uneven and affects the reflectance of long-wavelength light.
  • the backside recombination is increased; and the invention adopts a special water film, so that the etching amount on the back side of the silicon wafer is greater than or equal to 7 micrometers, and the water film at this time can protect the front PN junction very well.
  • a water film solution having a glucose content of 2.0 g/L and a sodium bisfluorosulfonimide content of 0.25 mol/L is prepared.
  • the silicon wafer processed by the step (1) is introduced into the etching bath, and the etching liquid is mixed with a common HF/HNO 3 /H 2 SO 4 acid. In the etching bath, the silicon wafer is floated on the etching liquid. Way to etch,
  • the etching amount on the back side of the silicon wafer was 8 ⁇ m.
  • Example 1 Pure water was used instead of the water film in Example 1, and the rest of the operation was the same as in Example 1, except that the etching amount on the back side of the silicon wafer was controlled to 5 ⁇ m. Compared to Example 1, the pile-forming polishing structure could not be completely removed, and the polished surface was not flat.
  • a water film solution having a glucose content of 2.0 g/L was prepared, and in order to make the viscosity of the water film at the same level as in Example 1 to avoid the error in comparison, sodium chloride was used in the present operation instead of the difluorosulfonate in Example 1. Sodium imide is added to the water film solution:
  • the water film described above was used in place of the water film of Example 1, and the rest of the operation was the same as in Example 1, and the etching amount on the back side of the silicon wafer was also 8 ⁇ m.
  • a water film solution having a sodium bisfluorosulfonimide content of 0.25 mol/L was prepared, and in order to make the viscosity of the water film at the same level as in Example 1 to avoid the error in comparison, sodium chloride was used instead of the example in the present operation.
  • the glucose in 1 is added to the water film solution:
  • the water film described above was used in place of the water film of Example 1, and the rest of the operation was the same as in Example 1, and the etching amount on the back side of the silicon wafer was also 8 ⁇ m.

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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

本发明属于太阳能电池技术领域，特别涉及一种太阳能电池硅片刻蚀用水膜溶液及其应用。本发明提供了一种太阳能电池硅片刻蚀用水膜溶液，该水膜溶液为葡萄糖和双氟磺酰亚胺盐分散于水中所形成，采用上述水膜溶液在硅片的扩散面(正面)上形成保护层，再进入刻蚀槽刻蚀背面和边缘的PN结，这样能够抑制刻蚀液中挥发的酸在水膜中的重新溶解，从而减小对扩散面(正表面)PSG和PN结的破坏。

Description

一种太阳能电池硅片刻蚀用水膜溶液及其应用 技术领域
本发明属于太阳能电池技术领域，特别涉及一种太阳能电池硅片刻蚀用水膜溶液及其应用。
背景技术
制造硅太阳能电池的一般方法是：首先将表面干净的P型或者N型硅片经过制绒工序形成绒面结构；其次在硅片表面扩散制结，形成N+或者P+的发射极，经过湿法刻蚀去掉硅片侧面和背面的扩散层；然后在其正表面再形成一层具有减反射功能的SiN薄膜；最后在硅片正背面分别制作金属电极，经过烧结过程形成晶硅太阳能电池。
其中，在湿法刻蚀前，一般需要采用水膜保护的方法，在硅片进入刻蚀槽前，在硅片正面喷一层水膜，防止药液翻液到硅片正面造成过刻而导致扩散面PN结遭到破坏。但问题在于：在用混酸进行刻蚀或抛光时，刻蚀槽中的高浓度酸(例如HF、硝酸等)易挥发，随着挥发量的增加挥发出来的酸会重新溶解在水膜中，对电池表面造成气相腐蚀，破坏了表面的PN结；其次，为了去除硅片背面的绒面形成背抛光结构，需要较大刻蚀量(一般指硅片背面的刻蚀量大于等于6微米时)，这也进一步加剧了对PN结的腐蚀破坏，单纯的水膜已经无法非常好地保护正面PN结了。
发明内容
本发明针对上述技术问题，提供了一种太阳能电池硅片刻蚀用水膜溶液，该水膜溶液为葡萄糖和双氟磺酰亚胺盐分散于水中所形成，
其中，葡萄糖在水膜溶液中的含量为1.5～4.0g/L，
双氟磺酰亚胺盐为双氟磺酰亚胺钠或双氟磺酰亚胺锂，其在水膜溶液中的含量为0.1～0.35mol/L，
该水膜溶液在制备过程中将各组分加入去离子水中搅拌均匀即可。
本发明还提供了一种上述水膜溶液的应用：
(1)采用上述水膜溶液在硅片的扩散面(正面)上形成保护层，
例如，通过水膜喷淋覆盖技术在扩散面上喷淋上述水膜，利用二氧化硅亲水性将水膜吸附在表面；
(2)将经过步骤(1)处理的硅片进入刻蚀槽，刻蚀背面和边缘的PN结，
在刻蚀槽中，硅片采用漂浮在刻蚀液上的方式进行刻蚀，或者采用带液滚轮将刻蚀液带到硅片背面进行刻蚀。
本发明的有益效果在于：本发明通过在水膜溶液中协同添加葡萄糖和双氟磺酰亚胺盐发现，这样能够抑制刻蚀液中挥发的酸在水膜中的重新溶解，从而减小对扩散面(正表面)PSG和PN结的破坏，且水膜溶液本身对扩散面及硅片基体无损害，葡萄糖作为天然绿色添加剂，本身不存在污染；
同时含有添加剂的水膜粘度略大于同等条件下的纯水粘度，而粘度的增大，促进了硅片边缘的表面张力相应变大，刻蚀时能一定程度上避免过刻；
由于现有技术中酸刻蚀的刻蚀量只能达到4～5微米，再增加腐蚀液的浓度或增加腐蚀时间则会对电池表面造成气相腐蚀，破坏表面的PN结，而4～5微米的刻蚀量对于一些背面具有绒面结构的硅片则很难完全除去这些绒面形成抛光结构，对于背钝化电池尤其明显，会造成抛光面不平整，影响对长波段光的反射率，同时会增大背面复合；而本发明采用了特殊的水膜，可以使得硅片背面的刻蚀量大于等于7微米，而且此时的水膜可以非常好地保护正面PN结。
具体实施方式
以下各实施例中所有操作均在常温(25℃)下进行：
实施例1
配制葡萄糖含量为2.0g/L、双氟磺酰亚胺钠含量为0.25mol/L的水膜溶液，
(1)通过水膜喷淋覆盖技术，于硅片表面经扩散制结而形成的扩散面上喷淋上述水膜形成平整的水膜保护层，该水膜保护层一直持续存在，直到硅片完成刻蚀步骤，
(2)将经过步骤(1)处理的硅片进入刻蚀槽，刻蚀液采用常用的HF/HNO3/H2SO4混酸，在刻蚀槽中，硅片采用漂浮在刻蚀液上的方式进行刻蚀，
硅片背面的刻蚀量为8微米。
对比实施例1
采用纯水代替实施例1中的水膜，其余操作均同实施例1，仅硅片背面的刻蚀量控制为5微米。相比于实施例1，无法完全除去绒面形成抛光结构，抛光面不平整。
对比实施例2
采用纯水代替实施例1中的水膜，其余操作均同实施例1，硅片背面的刻蚀量同样为8微米。
对比实施例3
配制葡萄糖含量为2.0g/L的水膜溶液，同时为了使水膜的粘度与实施例1在同一水平以避免对比时的误差，本操作中采用氯化钠代替实施例1中的双氟磺酰亚胺钠加入到水膜溶液中：
采用上述水膜代替实施例1中的水膜，其余操作均同实施例1，硅片背面的刻蚀量同样为8微米。
对比实施例4
配制双氟磺酰亚胺钠含量为0.25mol/L的水膜溶液，同时为了使水膜的粘度与实施例1在同一水平以避免对比时的误差，本操作中采用氯化钠代替实施例1中的葡萄糖加入到水膜溶液中：
采用上述水膜代替实施例1中的水膜，其余操作均同实施例1，硅片背面的刻蚀量同样为8微米。
将上述实施例和各对比实施例得到的硅片按照相同的现有技术制成电池片，然后检测各自的电性能，结果如下：
Figure PCTCN2017076574-appb-000001

Claims (7)

  1. 一种太阳能电池硅片刻蚀用水膜溶液，其特征在于：所述的水膜溶液为葡萄糖和双氟磺酰亚胺盐分散于水中所形成。
  2. 如权利要求1所述的太阳能电池硅片刻蚀用水膜溶液，其特征在于：所述的葡萄糖在水膜溶液中的含量为1.5～4.0g/L。
  3. 如权利要求1所述的太阳能电池硅片刻蚀用水膜溶液，其特征在于：所述的双氟磺酰亚胺盐为双氟磺酰亚胺钠或双氟磺酰亚胺锂，其在水膜溶液中的含量为0.1～0.35mol/L。
  4. 一种如权利要求1至3任一项所述的水膜溶液的应用，其特征在于：
    (1)采用所述的水膜溶液在硅片的扩散面上形成保护层；
    (2)将经过步骤(1)处理的硅片进入刻蚀槽，刻蚀背面和边缘的PN结。
  5. 如权利要求4所述的水膜溶液的应用，其特征在于：步骤(1)中，通过水膜喷淋覆盖技术在扩散面上喷淋所述水膜形成保护层。
  6. 如权利要求4所述的水膜溶液的应用，其特征在于：步骤(2)中，在刻蚀槽中，硅片采用漂浮在刻蚀液上的方式进行刻蚀。
  7. 如权利要求4所述的水膜溶液的应用，其特征在于：步骤(2)中，在刻蚀槽中，采用带液滚轮将刻蚀液带到硅片背面的方式进行刻蚀。
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