TWI526522B - Polycrystalline silicon wafer velvet additive, velveteen and its velvet method - Google Patents

Polycrystalline silicon wafer velvet additive, velveteen and its velvet method Download PDF

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TWI526522B
TWI526522B TW102148008A TW102148008A TWI526522B TW I526522 B TWI526522 B TW I526522B TW 102148008 A TW102148008 A TW 102148008A TW 102148008 A TW102148008 A TW 102148008A TW I526522 B TWI526522 B TW I526522B
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texturing
polycrystalline
additive
hno
aqueous solution
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TW201416418A (zh
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Li-Ming Fu
yuan-yuan Zhang
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    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
    • H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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    • 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
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
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    • 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
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
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    • 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 at least one potential-jump barrier or surface barrier
    • 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 at least one potential-jump barrier or surface barrier 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
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    • 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

Description

多晶矽片制絨添加劑、制絨液及其制絨方法
本發明涉及一種多晶矽片制絨添加劑、制絨液及其制絨方法。
在多晶矽太陽電池製造過程中，矽片表面制絨是關鍵的環節。制絨的效果直接影響了最終電池片的轉換效率和成品率。由於多晶矽片由不同晶向的晶粒組成，並且各個晶粒的晶向隨意分佈，因此，在一般制絨技術中多採用酸性溶液的濕化學腐蝕方法對多晶矽片表面進行制絨。該制絨技術基於酸性溶液對矽的各向同性腐蝕原理，在矽片不同晶粒表面形成相似的凹坑狀絨面，絨面的形貌與晶粒取向性無關。
目前，工業生產中常用的酸溶液由硝酸、氫氟酸和去離子水等組成。這種酸溶液的制絨效果並不是十分理想，存在的問題包括：絨面尺寸較大且均勻性不佳，不同晶粒之間色差比較明顯，存在宏觀形貌如黑線狀的深腐蝕坑，表面反射率較高，制絨穩定性不好。因此，如果可以通過在酸溶液中加入制絨添加劑，來解決上述問題，將具有重要的意義。
本發明的目的在於提供一種多晶矽片制絨添加劑、制絨液及其制絨方法，該多晶矽片制絨添加劑應用於多晶矽片的絨面製作，可以得到均勻性好、晶粒間無明顯色差的微洞型的微結構絨面，從而降低反射率，有效減少黑線產生數量；該多晶矽片制絨添加劑改變反應機理，控制反應速度，使制絨可以在接近室溫的條件下進行，大大降低溫度控制成本；還能有效去除滾輪印，使矽片更清潔，與後續製程更匹配，電池性能更穩定。
為實現上述目的，本發明提供一種多晶矽片制絨添加劑，其成分包括：檸檬酸三胺、聚乙烯吡咯烷酮(polyvinyl pyrrolidone)、 聚乙烯醇、檸檬酸和餘量的水。
較佳地，所述多晶矽片制絨添加劑中各組分的質量百分含量為：檸檬酸三胺0.2%~0.5%，聚乙烯吡咯烷酮0.1%~1%，聚乙烯醇0.1%~0.2%，檸檬酸2%~2.5%，餘量為水。較佳地，所述水為去離子水。
本發明還提供一種用於多晶矽片制絨的制絨液，其含有酸溶液和上述多晶矽片制絨添加劑，所述多晶矽片制絨添加劑與酸溶液的質量比為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HNO3水溶液；所述HF水溶液中含有49%的HF，所述HNO3水溶液中含有69%的HNO3；其中，所述百分比為質量百分比。
本發明還提供一種多晶矽片的制絨方法，利用上述制絨液對多晶矽片進行表面制絨。
較佳地，所述表面制絨的制絨溫度為5~25℃，制絨時間為45~180秒。
上述多晶矽片的制絨方法的具體步驟包括：1)配置制絨添加劑：將質量百分比為0.2%~0.5%的檸檬酸三胺、0.1%~1%的聚乙烯吡咯烷酮、0.1%~0.2%的聚乙烯醇、2%~2.5%的檸檬酸加入到餘量的水中，混合均勻配成制絨添加劑；其中水以去離子水為佳；2)配置制絨液：將步驟1製成的制絨添加劑加到酸溶液中，混合均勻配成制絨液；所述制絨添加劑與酸溶液的質量比為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HNO3水溶液；所述HF水溶液中含有49%的HF，所述HNO3水溶液中含有69%的HNO3；其中，所述百分比為質量百分比；3)將多晶矽片浸入步驟2製得的制絨液中進行表面制絨，制絨溫度為5~25℃，制絨時間為45~180秒。
本發明的優點和有益效果在於：提供一種多晶矽片制絨添加劑及其制絨方法，該多晶矽片制絨添加劑應用於多晶矽片的絨面製作，可以得到均勻性好、晶粒間無明顯色差的微洞型的微結構 絨面，從而降低反射率，有效減少黑線產生數量；該多晶矽片制絨添加劑改變反應機理，控制反應速度，使制絨可以在接近室溫的條件下進行，大大降低溫度控制成本；還能有效去除滾輪印，使矽片更清潔，與後續製程更匹配，電池性能更穩定。
圖1是本發明實施例3的多晶矽片表面絨面的掃描電子顯微鏡平面圖。
為使 貴審查委員能對本發明之特徵、目的及功能有更進一步的認知與瞭解，以下實施例特將本發明之系統的相關細部結構以及設計的理念原由進行說明，以使得 審查委員可以了解本發明之特點。
本實施例配合圖式，對本發明的具體實施方式作進一步描述。以下實施例僅用於更加清楚地說明本發明的技術方案，而不能以此來限製本發明的保護範圍。
本發明具體實施的技術方案是：
實施例1
一種多晶矽片的制絨方法，採取如下製程步驟：1)配製制絨添加劑：將0.2g檸檬酸三胺、0.1g聚乙烯吡咯烷酮、0.1g聚乙烯醇、2g檸檬酸溶解于去離子水中，得到100g制絨添加劑；2)配置制絨液：將7kg的HF水溶液(HF水溶液中HF的質量百分含量為49%)和25kg的HNO3水溶液(HNO3水溶液中HNO3的質量百分含量為69%)溶于去離子水中，得到100kg酸溶液；然後在該酸溶液中加入步驟1製成的100g制絨添加劑得到制絨液；3)制絨：將多晶矽電池片浸入制絨液中進行表面制絨，制絨溫度為5℃，制絨時間為180秒。
實施例2
一種多晶矽片的制絨方法，採取如下製程步驟：1)配製制絨添加劑：以去離子水為溶劑，將3g檸檬酸三胺、 6g聚乙烯吡咯烷酮、1.2g聚乙烯醇、15g檸檬酸溶解于去離子水中，得到600g制絨添加劑；2)配置制絨液：將14kg的HF水溶液(HF水溶液中HF的質量百分含量為49%)和50kg的HNO3水溶液(HNO3水溶液中HNO3的質量百分含量為69%)混合，得到100kg的酸溶液；然後在該酸溶液中加入步驟1製成的600g制絨添加劑得到制絨液；3)制絨：將多晶矽電池片浸入制絨液中進行表面制絨，制絨溫度為25℃，制絨時間為45秒。
實施例3
一種多晶矽片的制絨方法，採取如下製程步驟：1)配製制絨添加劑：以去離子水為溶劑，將1.2g檸檬酸三胺、1.5g聚乙烯吡咯烷酮、0.45g聚乙烯醇、6.9g檸檬酸溶解于去離子水中，得到300g制絨添加劑；2)配置制絨液：將10kg的HF水溶液(HF水溶液中HF的質量百分含量為49%)和40kg的HNO3水溶液(HNO3水溶液中HNO3的質量百分含量為69%)溶于去離子水中，得到100kg的酸溶液；然後在該酸溶液中加入步驟1製成的300g制絨添加劑得到制絨液；3)制絨：將多晶矽電池片浸入制絨液中進行表面制絨，制絨溫度為12℃，制絨時間為100秒。
圖1為本實施例3得到的多晶矽片表面絨面的掃描電子顯微鏡平面照片，從圖中可以看到制絨後在多晶矽片表面形成了微洞型的微結構絨面，絨面分佈比較均勻。
以上所述僅是本發明的較佳實施例，對於本技術領域具有通常知識的技術人員來說，在不脫離本發明技術原理的前提下，還可以做出若干改進和潤飾，這些改進和潤飾也應視為本發明的保護範圍。

Claims (7)

  1. 一種多晶矽片制絨添加劑，其特徵在於，其成分包括：檸檬酸三胺、聚乙烯吡咯烷酮、聚乙烯醇、檸檬酸和餘量的水。
  2. 如申請專利範圍第1項所述之多晶矽片制絨添加劑，其特徵在於，所述多晶矽片制絨添加劑中各組分的質量百分含量為：檸檬酸三胺0.2%~0.5%，聚乙烯吡咯烷酮0.1%~1%，聚乙烯醇0.1%~0.2%，檸檬酸2%~2.5%，餘量為水。
  3. 如申請專利範圍第1項或第2項所述之多晶矽片制絨添加劑，其特徵在於，所述水為去離子水。
  4. 一種用於多晶矽片制絨的制絨液，其特徵在於，其含有酸溶液和請求項3中的多晶矽片制絨添加劑，所述多晶矽片制絨添加劑與酸溶液的質量比為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HNO3水溶液；所述HF水溶液中含有49%的HF，所述HNO3水溶液中含有69%的HNO3；其中，所述百分比為質量百分比。
  5. 一種多晶矽片制絨方法，其特徵在於，利用請求項4所述的制絨液對多晶矽片進行表面制絨。
  6. 如申請專利範圍第5項所述之多晶矽片制絨方法，其特徵在於，所述表面制絨的制絨溫度為5~25℃，制絨時間為45~180秒。
  7. 如申請專利範圍第6項所述之多晶矽片制絨方法，其特徵在於，其具體步驟包括：1)配置制絨添加劑：將質量百分比為0.2%~0.5%的檸檬酸三胺、0.1%~1%的聚乙烯吡咯烷酮、0.1%~0.2%的聚乙烯醇、2%~2.5%的檸檬酸加入到餘量的水中，混合均勻配成制絨添加劑；2)配置制絨液：將步驟1製成的制絨添加劑加到酸溶液中，混合均勻配成制絨液；所述制絨添加劑與酸溶液的質量比為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HNO3水溶液；所述HF水溶液中含有49%的HF，所述HNO3 水溶液中含有69%的HNO3；其中，所述百分比為質量百分比；3)將多晶矽片浸入步驟2製得的制絨液中進行表面制絨，制絨溫度為5~25℃，制絨時間為45~180秒。
TW102148008A 2013-09-04 2013-12-24 Polycrystalline silicon wafer velvet additive, velveteen and its velvet method TWI526522B (zh)

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