本研究主旨係探討以金屬輔助化學蝕刻(Metal-assisted Chemical Etching)，結合複合式線鋸(Multi-wire Sawing)切割矽晶圓之可行性。首先以無電鍍法，在不鏽鋼基材上沉積鉑金屬膜作為催化金屬，再以混合物實驗設計法(Mixture design)找出蝕刻液的最佳配比。利用SEM與表面輪廓儀(Surface Profile)，觀察及測量於不同配比的蝕刻條件下，對矽晶圓的表面形態及蝕刻速率之影響。
研究結果發現以異丙醇與去離子水稀釋母鍍液後交替使用，可成功地在不鏽鋼基材表面，以無電鍍法沉積均勻且緻密的鉑層。蝕刻液之配方，則以配方比例為HF：H2O2：TFA= 4：4：4，可在(100)晶面與(111)晶面分別得到最佳的蝕刻速率16.348 m/min和7.699 m/min。

In this work, the feasibility to combine multi-wire sawing and metal-assisted chemical etching (MaCE) processes for silicon wafer cutting technology is studied. First, layers of Pt metal were deposited on stainless steel substrate via electroless plating method and the prepared material was used for the surface modification of silicon wafer by MaCE. Next, a mixture design method was adopt in order to facilitate the process of finding the best ratio among etchant chemicals. Finally, the effects caused by different etching conditions were evaluated by SEM and surface profile measurements.
It was found that uniform and dense Pt layers were successfully deposited on stainless steel by electroless plating, where the IPA and DI water diluted solutions were alternatively used in each plating cycle. As to the surface modification of silicon wafer by MaCE, the fastest etching rate was 16.348 m/min and 7.699 m/min respectively for (100) and (111) silicon, wherein the optimal combination of etchant chemicals was found HF：H2O2：TFA= 4：4：4.

[1] A. Grubler, "Global Energy Assessment—Toward a Sustainable Future. ," IIASA, Vienna, Austria and Cambridge University Press, Cambridge, UK and New York, NY, USA, http://www.iiasa.ac.at/web/home/resources/mediacenter/FeatureArticles/Sustainable.en.html 2012.
[2] M. Emst, "Global Average Temperature and Carbon Dioxide Concentration, 1880-2006. ," The Woods Holes Research Center, 2010.
[3] 陳華琳, "含磷混合加工液對多晶矽線切割放電品質特性之影響," 碩士學位, 機械工程學系, 國立中央大學, 2010.
[4] U. S. E. I. Administration, "Renewable Energy Consumption by Major Source," presented at the Annual Energy Review 2000.
[5] U. S. E. I. Administration, "Renewable Energy Consumption by Major Source," Annual energy review 2011, p. 278.
[6] REN21, "Renewables 2013 Global Status Report," Renewable Energy Policy Network for the 21st Century, p. 41, 2013.
[7] 蕭宏原著，陳啟文等人編譯, 半導體製程技術導論(修訂二版): 全華圖書股份有限公司, 2013.
[8] "Czochralski process," Wikipedia, 2015.
[9] A. C. Stephen著，呂學士，林佑昇譯, 半導體製程(第二版): 台商圖書有限公司, 2003.
[10] 曾樺樑，倪百祥, 電鍍工程手冊: 北京機械工業出版社, 2009.
[11] "電鍍基本原理與概念," http://my.stust.edu.tw/sys/read_attach.php?id=13217, 2003.
[12] 楊聰仁, "電鍍鎳與無電鍍鎳實驗," 材料基礎實驗(一), 2001.
[13] 葛明德, "無電鍍Ni/PTFE複合鍍層之研究," 博士學位, 化學工程系, 國立台灣科技大學, 2002.
[14] 神戶德藏著，莊萬發譯著, 無電解鍍金-化學鍍金技術: 復漢出版社, 1985.
[15] 許擇倫, "以無電鍍法製備純鈷金屬薄膜及空心奈米管之研究," 碩士學位, 化學工程與材料工程研究所, 國立中央大學, 2007.
[16] 曾俊傑，陳彥政等, "奈米鈀活化液應用於無電電鍍銅之研究," Journal of C.C.I.T., vol. 40, 2011.
[17] N. Feldstein, "Process for Metal Deposition of a Non-conductor Substrate " United States Patent, 1981.
[18] S. N. Paglieri, K. Y. Foo, J. D. Way, J. P. Collins, and D. L. Harper-Nixon, "A New Preparation Technique for Pd/Alumina Membranes with Enhanced High-temperature Stability," Industrial & Engineering Chemistry Research, vol. 38, pp. 1925-1936, 1999.
[19] 王榮霞，俞健等, "TiCl3/PdCl2法活化多孔陶瓷基體製備透氫Pd膜," Journal of Nanjing University of Technology (Natural Science Edition), vol. 33, 2011.
[20] H. B. Zhao, K. Pflanz, J. H. Gu, A. W. Li, N. Stroh, H. Brunner, et al., "Preparation of Palladium Composite Membranes by Modified Electroless Plating Procedure," Journal of Membrane Science, vol. 142, pp. 147-157, 1998.
[21] L. Q. Wu, N. Xu, and J. Shi, "Preparation of a Palladium Composite Membrane by an Improved Electroless Plating Technique," Industrial & Engineering Chemistry Research, vol. 39, pp. 342-348, 2000.
[22] R. C. Agarwala and S. Ray, "Variation of Structure in Electroless Ni-P Films With Phosphorus Content," Z. Metallkd., vol. 79, pp. 472-475, 1988.
[23] I. Ohno, "Electroless Deposition of Palladium and Platinum," Modern Electroplating, Fifth Edition, pp. 477-482, 2010.
[24] R. N. Rhoda and R. F. Vines, "Bath and Process for Platinum and Platinum Alloys," United States Patent, 1969.
[25] F. H. Leaman and C. W. Walter, "Method and Composition for Platinum Plating and Articles Plated Therewith," United States Patent, 1971.
[26] A. S. Koslov, T. Palanisamy, and D. Narasimhan, "Electroless Autocatalytic Platinum Plating," United States Patent, 2002.
[27] C. R. Rao and M. Pushpavanam, "Electroless Deposition of Platinum on Titanium Substrates," Materials Chemistry and Physics, vol. 68, pp. 62-65, 2001.
[28] F. Leaman, "Deposition of Pt by Chemical Reduction of Aqueous Solutions," Plating, vol. 59, pp. 440-444, 1972.
[29] C. Robin and K. W. Zhong, "Immersion Platium Plating Solution," United States Patent, 2011.
[30] B. Kong, L. Lvanov, Z. W. Sun, and J. Tong, "Electroless Deposition of Platinum on Copper," United States Patent, 2013.
[31] D. Turner and P. Holmes, "The Electrochemistry of Semiconductors," by PJ Holmes (Academic Press, London and New York, 1962) p, vol. 155, 1962.
[32] MEMSnet, https://www.memsnet.org/mems/processes/etch.html.
[33] H. Lv, H. Shen, Y. Jiang, C. Gao, H. Zhao, and J. Yuan, "Porous-pyramids Structured Silicon Surface with Low Reflectance Over a Broad Band by Electrochemical Etching," Applied Surface Science, vol. 258, pp. 5451-5454, 2012.
[34] A. Chu, J. Wang, Z. Tsai, and C. Lee, "A Simple and Cost-effective Approach for Fabricating Pyramids on Crystalline Silicon Wafers," Solar Energy Materials and Solar Cells, vol. 93, pp. 1276-1280, 2009.
[35] X. Li, B. K. Tay, P. Miele, A. Brioude, and D. Cornu, "Fabrication of Silicon Pyramid/Nanowire Binary Structure with Superhydrophobicity," Applied Surface Science, vol. 255, pp. 7147-7152, 2009.
[36] H. Seidel, L. Csepregi, A. Heuberger, and H. Baumgärtel, "Anisotropic Etching of Crystalline Silicon in Alkaline Solutions I. Orientation Dependence and Behavior of Passivation Layers," Journal of the Electrochemical Society, vol. 137, pp. 3612-3626, 1990.
[37] 許鈞皓, "金字塔結構之矽基太陽能電池特性研究," 碩士學位, 電子工程學系, 國立台灣科技大學, 2012.
[38] D. Dimova-Malinovska, M. Sendova-Vassileva, N. Tzenov, and M. Kamenova, "Preparation of Thin Porous Silicon Layers by Stain Etching," Thin Solid Films, vol. 297, pp. 9-12, 1997.
[39] S. Chattopadhyay, X. Li, and P. W. Bohn, "In-plane Control of Morphology and Tunable Photoluminescence in Porous Silicon Produced by Metal-assisted Electroless Chemical Etching," Journal of Applied Physics, vol. 91, pp. 6134-6140, 2002.
[40] Z. Huang, N. Geyer, P. Werner, J. De Boor, and U. Gösele, "Metal‐assisted Chemical Etching of Silicon: A Review," Advanced Materials, vol. 23, pp. 285-308, 2011.
[41] V. Lehmann, "Electrochemistry of Silicon: Instrumentation, Science, Materials and Applications," Wiley-VCH, ISBN 3-527-29321-3., vol. 1, 2002.
[42] 張瀚丞, "在HF水溶液中氧化劑和溫度對奈米線形成速率及微結構之影響," 碩士學位, 材料科學及工程研究所, 國立成功大學, 2008.
[43] K. Peng and J. Zhu, "Morphological Selection of Electroless Metal Deposits on Silicon in Aqueous Fluoride Solution," Electrochimica Acta, vol. 49, pp. 2563-2568, 2004.
[44] M. L. Zhang, K. Q. Peng, X. Fan, J. S. Jie, R. Q. Zhang, S. T. Lee, et al., "Preparation of Large-area Uniform Silicon Nanowires Arrays Through Metal-assisted Chemical Etching," The Journal of Physical Chemistry C, vol. 112, pp. 4444-4450, 2008.
[45] Y. Hu, K. Q. Peng, L. Liu, Z. Qiao, X. Huang, X. L. Wu, et al., "Continuous-flow Mass Production of Silicon Nanowires via Substrate-Enhanced Metal-Catalyzed Electroless Etching of Silicon with Dissolved Oxygen as an Oxidant," Scientific reports, vol. 4, 2014.
[46] 梁峻碩, "線鋸切割太陽能基板之研究," 碩士學位, 機械工程系, 國立台灣科技大學, 2008.
[47] 陳炤彰，趙培勛, "線鋸切削製程鋸削太陽能電池矽基板之文獻回顧."
[48] 李志士，黃彥傑等, "鑽石顆粒電鍍於切割線之研究," presented at the 國立勤益科技大學 2013 綠色科技工程與應用研討會(GTEA), 2013.
[49] 沈岳文, "游離再生磨粒線切割加工對矽晶圓品質特性之研究," 碩士學位, 機械工程系, 國立雲林科技大學, 2004.
[50] M. A. Costantini and J. A. Talbott, "Method and Apparatus for Improved Wire Saw Slurry," United States Patent, 2000.
[51] 廖運炫，許春耀, "脆性材料線鋸切割," in 機械工業雜誌, ed, 2002, pp. 122-129.
[52] K. Kajimoto, "Slurry Recycling Method," United States Patent, 2005.
[53] H. T. T. Kawasaki, "Multi-wire Saw," United States Patent, 2007.
[54] T. Enomoto, Y. Shimazaki, Y. Tani, M. Suzuki, and Y. Kanda, "Development of a Resinoid Diamond Wire Containing Metal Powder for Slicing a Slicing Ingot," CIRP Annals-Manufacturing Technology, vol. 48, pp. 273-276, 1999.
[55] W. Clark, A. Shih, C. Hardin, R. Lemaster, and S. McSpadden, "Fixed Abrasive Diamond Wire Machining—Part I: Process Monitoring and Wire Tension Force," International Journal of Machine Tools and Manufacture, vol. 43, pp. 523-532, 2003.
[56] 鄭嘉葳, "樹脂燒結固定磨粒鑽石線鋸切割矽晶棒之特性研究," 碩士學位, 動力機械工程研究所, 國立清華大學, 2005.
[57] 宋健民. (2006) 台灣鑽石技術之大躍進. 機械工業雜誌. 43-51.
[58] 宋健民. (2006) 鑽石陣鑽石鋸齒. 機械工業雜誌. 92-97.
[59] P. Wei, L. Fuqing, and Y. Chunyan, "Research on the Ultraviolet-curing Resin Wire Saw," 2006.
[60] 萬惠雯, "研調:太陽能矽晶圓鑽石切割技術邁入商業化," http://www.moneydj.com/KMDJ/News/NewsViewer.aspx?a=c53a3667-0271-43bf-9c66-c6a352d40a62, 2011.