本研究結合膠體顯影與金屬輔助化學蝕刻技術製作可調間距陣列圖案，目的是要開發一具次微米/奈米級且寬間距(>1μm)的陣列圖案。利用自組裝的原理，將PMSQ(polymethylsilsesquioxane)微米球分散在空氣-水介面，接著讓這些微米球排列在已塗佈高分子的矽基板上，加熱至高分子熔點(Tm)，目的是讓PMSQ沉入高分子中； 移除掉PMSQ球後，便以乾蝕刻小心地去除原先球底部殘留的高分子層，在適當的乾蝕刻參數下，可得到各種不同大小所暴露出矽基板的圓形陣列圖案，然後再用金屬輔助化學蝕刻法進行非等向性蝕刻所暴露出的矽基板。另外，以電子束蒸鍍法沉積金屬於基板上後，再以丙酮洗去高分子，留在洞內的金屬便可成為乾蝕刻的光罩，在適當的乾蝕刻參數下，可調間距陣列圖案便可得到。目前已成功開發大面積(>10cm)和可調間距(非緊密排列)陣列圖案，此技術有很大的應用潛力於光電元件、顯示器、發光二極體與太陽能電池等。

This research describes a novel technique for fabricating pitch-adjustable arrayed patterns on silicon substrate using colloidal lithography process assisted with metal-assisted chemical etching. Large-area PMSQ (polymethylsilsesquioxane) sphere arrays were first obtained at the air-water interface, and then adsorbed onto a substrate coated with a layer of polymer adhesive. Heating was further used to sink PMSQ spheres into the adhesive. After removing the PMSQ spheres and employing reactive ion etching (RIE) to carefully control the etching of the residual film, we could vary the sizes of the circular patterns of exposed silicon surface in arrays. Metal-assisted chemical etching process was further employed to selectively etch only the exposed silicon surface. We have established a strategy to successfully prepare the pitch-adjustable (non-closest-packing) arrayed patterns in large area (>10 cm). The method developed here has large application potentials in optical devices, displays, light-emitting diodes, solar cells, etc…

[1] W. Waido, "Techniques and Tools for Optical Lithography" in Handbook of VLSI Microlithography Principles, Technology and Applications,edited by W.B. Glendinning and J. N. Helbert,Noyes Publications (1991).
[2] C. H. Ting, M. Hatzakis, and R. A. Leone, "Fabrication of Microelectronic Devices with Electron-Beam Lithography," Journal of Vacuum Science & Technology 12 (6), 1304-1304 (1975).
[3] H. Ahmed, "Electron-Beam Lithography for Microcircuit Fabrication," Electronics and Power 22 (7), 433-436 (1976).
[4] N. D. Denkov. D. Velev, P. A. Kralchevsky, I. B. Ivanov, H. Yoshimura, and K. Nagayama, “Mechanism of Formation of Two-Dimensional Crystals from Latex Particles on Substrates”, Langmuir ,8,3183-3190(1992).
[5] R. Micheletto, H. Fukuda, and M. Ohtsu,“A Simple Method for the Production of a Two-Dimensional Ordered Array of Small Latex Particles”, Langmuir , 11, 3333-3336(1995).
[6] S. Rakers, L. F. Chi, and H. Fuchs, “Influence of the Evaporation Rate on the Packing Order of Polydisperse Latex Monofilms”, Langmuir, 13, 7121 – 7124(1997).
[7] John C. Hulteen and Richard P. Van Duyne,“Nanosphere lithography: A materials general fabrication process for periodic particle array surfaces“, J. Vac. Sci. Technol. A, 13,3,1553-1558(1995).
[8] M. Kondo, K. Shinozaki, L. Bergstrom, N. Mizutani, “Preparation of Colloidal Monolayers of Alkoxylated Silica Particles at the Air-Liquid Interface ”, Langmuir, 11, 394( 1995).
[9] J. Rybczynski, U. Ebels, M. Giersig,“Large-scale, 2D arrays of magnetic nanoparticles”, Colloids and Surfaces A: Physicochem. Eng. Aspects, 219 , 1-6(2003).
[10] Seung-Man Yang, Se Gyu Jang, Dae-Geun Choi, Sarah Kim, and HyungKyun Yu,“Nanomachining by Colloidal Lithography”, small, 2, No. 4, 458 – 475(2006).
[11] C. L. Cheung, R. J. Nikoli´c, C. E. Reinhardt and T. F. Wang, “Fabrication of nanopillars by nanosphere lithography”, Nanotechnology, 17,1339–1343(2006).
[12] Benzhong Wang, Wei Zhao, Ao Chen, Soo-Jin Chua,“ChuaFormation of nanoimprinting mould through use of nanosphere lithography”,Journal of Crystal Growth, 288, 200–204(2006).
[13] Difu Zhu, He Huang, Gang Zhang, Xun Zhang, Xiao Li, Xuemin Zhang, Tieqiang Wang, and Bai Yang,“Fabrication of Heterogeneous Double-Ring-Like Structure Arrays by Combination of Colloidal Lithography and Controllable Dewetting”, Langmuir, 28(5),2873–2880(2012).
[14] 陳秀春,“SF6-O2氣體的非等向性矽蝕刻技術, 光學工程, 第八十三期,73-78(2003).
[15] V. Ovchinnikov*, A. Malinin, S. Novikov, C. Tuovinen,“Fabrication of silicon nanopillars using self-organized gold–chromium mask”, Materials Science and Engineering, B69–70, 459–463 (2000).
[16] Daniel. L. Flamm,“Mechanisms of silicon etching in fluorine- and chlorine-containing plasmas”, Pure & Appl. Chem., Vol. 62, No. 9, pp. 1709-1720(1990).
[17] Ut-Binh T. Giang, Dooyoung Lee, Michael R. King and Lisa A. DeLouise,“Microfabrication of cavities in polydimethylsiloxane using DRIE silicon molds”, Lab Chip,7, 1660–1662(2007).
[18] Mark Kiehlbauch, Eray S. Aydil, Sergi Gomez and Rodolfo Jun Belen,“Etching of high aspect ratio structures in Si using SF6/O2 plasma”, J. Vac. Sci. Technol. A, 22(3), 606-615(2004).
[19] T. Wells, M. M. El-Gomati, and J. Wood,“Low temperature
reactive ion etching of silicon with SF6/O2 plasmas”, J. Vac. Sci. Technol. B 15(2), 434-438(1997).
[20] R. F. Figueroa, S. Spiesshoefer, S. L. Burkett, and L. Schaper,“Control of sidewall slope in silicon vias using SF6/O2 plasma etching in a conventional reactive ion etching tool”, J. Vac. Sci. Technol. B 23, 2226 (2005)
[21] Y. Xu, H.-B. Sun, J.-Y. Ye, S. Matsuo, H. Misawa,
“Two-Dimensional Ceramic Photonic Crystals Fabricated by a
Solution Method”J. Opt. Soc. Am., B 18, 1084 (2001).
[22] W. Hattori, H. Someya, M. Baba, H. Kawaura,“Size-based
continuous-flow directional control of DNA with a nano-pillar
anisotropic array” J. Chromatogr. A1051,141 (2004)
[23] X.-M. Yan, S. Kwon, A.M. Contreras, M.M. Koebel, J. Bokor, G.A. Somorjai, “Fabrication of Dense Arrays of Platinum Nanowires on Silica, Alumina, Zirconia and Ceria Surfaces as 2-D Model Catalysts ”Catal. Lett. 105, 127 (2005).
[24] y.-f. chang, q.-r. chou, j.-y. lin, c.-h. lee, “Fabrication of high-aspect-ratio silicon nanopillar arrays with the conventional reactive ion etching technique”, Appl. Phys., A 86, 193–196 (2007).
[25] R. d’Agostino, D.L. Flamm, J. Appl. Phys. 52, 162 (1981).
[26] H. Jansen, M. de Boer, R. Legtenberg, M. Elwenspoek,“The black silicon method: a universal method for determining the parameter setting of a fluorine-based reactive ion etcher in deep silicon trench
etching with profile control”J. Micromech. Microeng. 5, 115(1995)
[27] 龍柏華,“濕蝕刻製程介紹暨機台原理簡介”, 光連雙月刊, 48期,37-41 (2003).
[28] Kuiqing Peng, Yunjie Yan, Shangpeng Gao, and jing
Zhu,“Dendrite-Assisted Growth of Silicon Nanowires in Electroless Metal Deposition”, Adv. Funct. Mater., 13, 127-132(2003).
[29] Kuiqing Peng, Zhipeng Huang, and jing Zhu,“Fabrication of Large-Area Silicon Nanowire p-n Junction Diode Arrays”, Adv. Mater., 16, 73-76(2004).
[30] Kuiqing Peng, Zhipeng Huang, and jing Zhu,“Synthesis of
Large-Area Silicon Nanowires Arrays via Self-Assembling
Nanoelectrochemistry”, Adv. Mater, 14, 1164-1167(2002).
[31] C. Chartier, S. Bastide, C. Le’vy-Cle’ment,“Metal-assisted chemical etching of silicon in HF–H2O2”, Electrochimica Acta, 53, 5509–5516(2008).
[32] Dae Ho Lee, Yongkwan Kim, Gregory S. Doerk, Ian Laboriante and Roya Maboudian,“Strategies for controlling Si nanowire formation during Au-assisted electroless etching”, J. Mater. Chem., 21,10359(2011).
[33] Shih-Wei Chang, Vivian P. Chuang, Steven T. Boles, Caroline A. Ross, and Carl V. Thompson,“Densely Packed Arrays of Ultra-High-Aspect-Ratio Silicon Nanowires Fabricated using Block-Copolymer Lithography and Metal-Assisted Etching”,Adv. Funct. Mater., 19, 2495–2500(2009).
[34] Pradeep Sharma, and Yuh-Lin Wang, Directional Etching of Silicon by Silver Nanostructures, Applied Physics Express, 4 ,025001 (2011).
[35] Zhipeng Huang, Hui Fang, and Jing Zhu,“Fabrication of Silicon Nanowire Arrays with Controlled Diameter, Length, and Density”, Adv. Mater., 19, 744–748 (2007).
[36] Hsin-Ping Wang, Kun-Yu Lai, Yi-Ruei Lin, Chin-An Lin, and Jr-Hau He,“Periodic Si Nanopillar Arrays Fabricated by Colloidal Lithography and Catalytic Etching for Broadband and Omnidirectional Elimination of Fresnel Reflection”, Langmuir, 26(15), 12855–12858(2010).
[37] W. L. Brown, T. Venkatesan, and A. Wagner,
"Ion-Beam Lithography," Nuclear Instruments & Methods in
Physics Research 191 (1-3), 157-168 (1981).
[38] T. W. Barbee, "Multilayer Optics for the Soft-X-Ray and Extreme Ultra-Violet," Phys. Scr. T31, 147-153 (1990).
[39] Stephen Y. Chou, Peter R. Krauss, and Preston J. Renstrom,“Nanoimprint lithography”, J. Vac. Sci. Technol. B 14(6), 4129-4133(1996).
[40] Younan Xia, Dong Qin, and George M. Whitesides,“Microcontact Printing with a Cylindrical Rolling Stamp: A Practical Step Toward Automatic Manufacturing of Patterns with Submicrometel. Sized Features”, Adv. Mater. 8, No, 121015-1017(1996)
[41] T. W. Odom, J. C. Love, D. B. Wolfe, K. E. Paul, G. M. Whitesides,“Improved Pattern Transfer in Soft Lithography Using Composite Stamps”Langmuir 18, 5314 (2002)
[42] T. W. Odom, V. R. Thalladi, J. C. Love, G. M. Whitesides,“Generation of 30−50 nm Structures Using Easily Fabricated, Composite PDMS Masks“J. Am. Chem. Soc., 124, 12112 (2002)
[43] H-W Li, B. V. O. Muir, G. Fichet, W. T. S. Huck,“Nanocontact Printing:  A Route to Sub-50-nm-Scale Chemical and Biological Patterning“ Langmuir, 19,1963 (2003)
[44] X. D. Huang, L.-R. Bao, X. Cheng, L. J. Guo, S. W. Pang et al.,“Reversal imprinting by transferring polymer from mold to substrate” J. Vac. Sci. Technol. B 20, 2872 (2002).
[45] 謝信宏, “奈米多孔模具製備及其在壓印技術上之應用”, 國立成功大學化學工程學系碩士論文, 1-121 (1999).
[46] 謝俊仰,“改良式逆壓印技術應用於無殘餘曾圖案轉移”,國立成功大學化學工程學系碩士論文, 1-155 (1997).
[47] Xin Yan, Jimin Yao, Guang Lu, Xiao Li, Junhu Zhang, Kun Han, and Bai Yang*,“Fabrication of Non-Close-Packed Arrays of Colloidal Spheres by Soft Lithography” ,J. AM. CHEM. SOC. 127, 7688-7689 (2005)
[48] Iskender Yilgor*, Sevilay Bilgin, Mehmet Isik, Emel Yilgor,“Facile preparation of superhydrophobic polymer surfaces” , Polymer, 53,1180e1188 (2012) .
[49] D.Y. Kwok1, 1, A.W. Neumann,“Contact angle measurement and contact angle interpretation” , Advances in Colloid and Interface Science, 81, 167–249 (1999) .