本實驗係對多層石墨烯表面進行官能基化(Functionalization)處理，並於表面鍍著氧化錫後，予以還原處理以製備石墨烯/錫複合材料。本實驗合成石墨烯/錫複合材料之過程，首先將市售之多層石墨烯在氧環境下進行熱處理，使得石墨烯表面引入官能基團，即氧化石墨烯。繼以溶液共混方式以SnCl2和HCl在氧化石墨烯表面鍵結SnO2以形成石墨烯/二氧化錫。後續以兩種方法還原石墨烯/二氧化錫，第一種方法只利用95%N2/5%H2混合氣體；第二種方法利用甲烷 (CH4) ，有效將二氧化錫還原成錫。此外，為了得到更多的純錫本研究嘗試利用單步驟還原法，即置於高溫927oC甲烷(CH4)環境下持溫2小時，以及雙步驟還原法，即利用95%N2/5%H2混合氣體於200oC持溫5小時後，繼續利用甲烷(CH4)於高溫927oC持溫2小時實驗證實雙步驟還原法比單步驟還原效果佳。考慮現今電子產品對導熱和散熱的需求，本研究進一步將原始石墨烯粉末與石墨烯/錫粉末壓錠並燒結，製備成複合錠材進行熱傳導率的量測；量測結果顯示，因石墨烯/錫無法達到預期之緻密性與均勻性，原始石墨烯不論平行方向或垂直方向熱傳導都優於石墨烯/錫，同時也低於預測之熱傳導值。

This study tried to prepare the composite material structure consisting of Sn particles and multilayer graphene nanosheets. The pristine multilayer graphene surface was firstly functionalized by heat treatment under oxygen environment to produce graphene oxide, followed by blending with SnCl2 and HCl chemical solution to allow graphene oxide surface bonded with SnO2 to form graphene/tin oxide. The reduction of the tin oxide was conducted with two different graphene/tin dioxide reduction methods using 95% N2 / 5% H2 forming gas or methane (CH4) as reducing agent. The results showed that CH4 effectively reduced SnO2 to Sn compared with 95% N2 / 5% H2 forming gas. This study also applied single-step reduction method under 927 oC methane environment for 2 hours and two-step reduction method under 200 oC 95% N2 / 5% H2 forming gas for 5 hours, followed by reduction under 927 oC methane environment for 2 hours, The experiment confirmed that the two-step reduction method was better than the single-step reduction. Considering the current demand for thermal and heat dissipation of electronic equipment, the pristine graphene powder and graphene/tin powder were further made into pellet separately for heat conductivity measurement. The results showed that the heat conductivity of pristine graphene and Graphene/Sn pellet, either parallel or vertical direction, has thermal conductivity lower than the predicted value for the reason of not achieving the expected density and uniformity.

A. Hirsch, "The Era of Carbon Allotropes," Nature Materials, vol. 9, no. 11, pp. 868-871, 2010.
[2] H. W. Kroto, J. R. Heath, S. C. O'Brien, R. F. Curl, and R. E. Smalley, "C60: Buckminsterfullerene," Nature, vol. 318, no. 6042, pp. 162-163, 1985.
[3] 李偉立, "2010年諾貝爾物理獎—碳奈米結構的美," 科學發展, vol. 462, pp.54-59, 2011.
[4] 陳永勝、黃毅, 石墨烯新型二維奈米材料. 中國: 科學出版社,pp.1-19, 2013.
[5] S. Iijima, "Helical Microtubules of Graphitic Carbon," Nature, vol. 354, no. 6348, pp. 56-58, 1991.
[6] J. Hone, B. Batlogg, Z. Benes, A. T. Johnson, and J. E. Fischer, "Quantized Phonon Spectrum of Single-Wall Carbon Nanotubes," Science, vol. 289, no. 5485, pp. 1730-1733, 2000.
[7] S. Iijima and T. Ichihashi, "Single-Shell Carbon Nanotubes of 1-nm Diameter," Nature, vol. 363, no. 6430, pp. 603-605, 1993.
[8] P. R. Bandaru, "Electrical Properties and Applications of Carbon Nanotube Structures," Journal of Nanoscience and Nanotechnology, vol. 7, no. 4-5, pp. 1239-1267, 2007.
[9] T. Dürkop, S. A. Getty, E. Cobas, and M. S. Fuhrer, "Extraordinary Mobility in Semiconducting Carbon Nanotubes," Nano Letters, vol. 4, no. 1, pp. 35-39, 2004.
[10] J. Hone, "Carbon Nanotubes: Thermal Properties," Journal of Nanoscience and Nanotechnology, vol. 6, pp. 603-610, 2004.
[11] P. G. Collins and P. Avouris, "Nanotubes for Electronics," Scientific American, vol. 283, no. 6, pp. 62-69, 2000.
[12] 黃建盛, "奈米碳管簡介," 科學新天地, vol. 第十三期, pp. 4-9, 2006.
[13] H. P. Boehm, R. Setton, and E. Stumpp, "Nomenclature and Terminology of Graphite Intercalation Compounds (IUPAC Recommendations 1994)," Pure and Applied Chemistry, vol. 66, no. 9, pp. 1893-1901, 1994.
[14] K. S. Novoselov, "Electric Field Effect in Atomically Thin Carbon Films," Science, vol. 306, no. 5696, pp. 666-669, 2004.
[15] K. P. Loh, Q. Bao, P. K. Ang, and J. Yang, "The Chemistry of Graphene," Journal of Materials Chemistry, vol. 20, no. 12, pp. 2277-2289, 2010.
[16] Y. Kopelevich and P. Esquinazi, "Graphene Physics in Graphite," Advanced Materials, vol. 19, no. 24, pp. 4559-4563, 2007.
[17] A. H. R. H. M. G. S. D. King, "Synthèses Dans La Série Des Dérivés Polycycliques Aromatiques Hautement Condensés. L'hexabenzo-1,12; 2,3; 4,5; 6,7; 8,9; 10,11-Coronène, Le Tétrabenzo-4,5; 6,7; 11,12; 13,14-Péropyrène Et Le Tétrabenzo-1,2; 3,4; 8,9; 10,11-Bisanthène," Helvetica Chimica Acta, vol. 41, no. 5, pp. 1177--1183, 1958.
[18] D. R. Cooper, "Experimental Review of Graphene," ISRN Condensed Matter Physics, vol. 2012, pp.1-56, 2012.
[19] J.-N. Fuchs and M. O. Goerbig, "Introduction to The Physical Properties of Graphene," Lecture Notes, pp.10-15, 2008.
[20] L. P. Biró, P. Nemes-Incze, and P. Lambin, "Graphene: Nanoscale Processing and Recent Applications," Nanoscale, vol. 4, no. 6, pp. 1824-1839, 2012.
[21] 劉偉仁, 石墨烯技術. 台灣:五南出版,pp.283-342,2015.
[22] Y. H. Hu, H. Wang, and B. Hu, "Thinnest Two-Dimensional Nanomaterial—Graphene for Solar Energy," ChemSusChem, vol. 3, no. 7, pp. 782-796, 2010.
[23] C.-H. Park, L. Yang, Y.-W. Son, M. L. Cohen, and S. G. Louie, "Anisotropic Behaviours of Massless Dirac Fermions in Graphene Under Periodic Potentials," Nature Physics, vol. 4, no. 3, pp. 213-217, 2008.
[24] G. W. Semenoff, "Condensed-Matter Simulation of A Three-Dimensional Anomaly," Physical Review Letters, vol. 53, no. 26, p. 2449, 1984.
[25] P. Avouris, Z. Chen, and V. Perebeinos, "Carbon-Based Electronics," Nature Nanotechnology, vol. 2, no. 10, pp. 605-615, 2007.
[26] K. S. Novoselov, "Two-Dimensional Gas of Massless Dirac Fermions in Graphene," Nature, vol. 438, no. 7065, pp. 197-200, 2005.
[27] M. J. Allen, V. C. Tung, and R. B. Kaner, "Honeycomb Carbon: A Review of Graphene," Chemical Reviews, vol. 110, no. 1, pp. 132-145, 2009.
[28] Y. Zhang, Y.-W. Tan, H. L. Stormer, and P. Kim, "Experimental Observation of The Quantum Hall Effect And Berry's Phase in Graphene," Nature, vol. 438, no. 7065, pp. 201-204, 2005.
[29] T. Ando, "The Electronic Properties of Graphene and Carbon Nanotubes," NPG Asia Materials, vol. 1, no. 1, pp. 17-21, 2009.
[30] C. Lee, X. Wei, J. W. Kysar, and J. Hone, "Measurement of The Elastic Properties and Intrinsic Strength of Monolayer Graphene," Science, vol. 321, no. 5887, pp. 385-388, 2008.
[31] I. Ovid'ko, "Mechanical Properties of Graphene," Reviews on Advanced Materials Science, vol. 34, no. 1, pp. 1-11, 2013.
[32] I. Frank, D. M. Tanenbaum, A. Van der Zande, and P. L. McEuen, "Mechanical Properties of Suspended Graphene Sheets," Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena, vol. 25, no. 6, pp. 2558-2561, 2007.
[33] D. A. Dikin et al., "Preparation and Characterization of Graphene Oxide Paper," Nature, vol. 448, no. 7152, pp. 457-460, 2007.
[34] E. F. Sheka, "The Uniqueness of Physical And Chemical Natures of Graphene: Their Coherence and Conflicts," International Journal of Quantum Chemistry, vol. 114, no. 16, pp. 1079-1095, 2014.
[35] A. Barinov, "Initial Stages of Oxidation On Graphitic Surfaces: Photoemission Study and Density Functional Theory Calculations," The Journal of Physical Chemistry C, vol. 113, no. 21, pp. 9009-9013, 2009.
[36] W. Cai, "Synthesis and Solid-State NMR Structural Characterization of 13C-Labeled Graphite Oxide," Science, vol. 321, no. 5897, pp. 1815-1817, 2008.
[37] H.-K. Jeong, "Evidence of Graphitic AB Stacking Order of Graphite Oxides," Journal of the American Chemical Society, vol. 130, no. 4, pp. 1362-1366, 2008.
[38] A. A. Balandin, "Superior Thermal Conductivity of Single-Layer Graphene," Nano Letters, vol. 8, no. 3, pp. 902-907, 2008.
[39] J. Hone, M. Whitney, C. Piskoti, and A. Zettl, "Thermal Conductivity of Single-Walled Carbon Nanotubes," Physical Review B, vol. 59, no. 4, p. R2514, 1999.
[40] P. Kim, L. Shi, A. Majumdar, and P. McEuen, "Thermal Transport Measurements of Individual Multiwalled Nanotubes," Physical Review Letters, vol. 87, no. 21, p. 215502, 2001.
[41] A. Lerf, H. He, M. Forster, and J. Klinowski, "Structure of Graphite Oxide Revisited," The Journal of Physical Chemistry B, vol. 102, no. 23, pp. 4477-4482, 1998.
[42] T. Anthony, J. Fleischer, J. Olson, and D. G. Cahill, "The Thermal Conductivity of Isotopically Enriched Polycrystalline Diamond Films," Journal of Applied Physics, vol. 69, no. 12, pp. 8122-8125, 1991.
[43] L. Wei, P. Kuo, R. Thomas, T. Anthony, and W. Banholzer, "Thermal Conductivity of Isotopically Modified Single Crystal Diamond," Physical Review Letters, vol. 70, no. 24, p. 3764, 1993.
[44] B. C. Brodie, "On The Atomic Weight of Graphite," Philosophical Transactions of the Royal Society of London, vol. 149, pp. 249-259, 1859.
[45] M. Hirata, T. Gotou, S. Horiuchi, M. Fujiwara, and M. Ohba, "Thin-Film Particles of Graphite Oxide 1: High-Yield Synthesis and Flexibility of The Particles," Carbon, vol. 42, no. 14, pp. 2929-2937, 2004.
[46] W. S. Hummers Jr and R. E. Offeman, "Preparation of Graphitic Oxide," Journal of the American Chemical Society, vol. 80, no. 6, pp. 1339-1339, 1958.
[47] C. Shan, H. Yang, J. Song, D. Han, A. Ivaska, and L. Niu, "Direct Electrochemistry of Glucose Oxidase and Biosensing for Glucose Based on Graphene," Analytical Chemistry, vol. 81, no. 6, pp. 2378-2382, 2009.
[48] J. Shen, Y. Hu, C. Li, C. Qin, M. Shi, and M. Ye, "Layer-By-Layer Self-Assembly of Graphene Nanoplatelets," Langmuir, vol. 25, no. 11, pp. 6122-6128, 2009.
[49] G. Srinivas, Y. Zhu, R. Piner, N. Skipper, M. Ellerby, and R. Ruoff, "Synthesis of Graphene-Like Nanosheets and Their Hydrogen Adsorption Capacity," Carbon, vol. 48, no. 3, pp. 630-635, 2010.
[50] M. Zhou, Y. Zhai, and S. Dong, "Electrochemical Sensing and Biosensing Platform based on Chemically Reduced Graphene Oxide," Analytical Chemistry, vol. 81, no. 14, pp. 5603-5613, 2009.
[51] L. Zhang, X. Li, Y. Huang, Y. Ma, X. Wan, and Y. Chen, "Controlled Synthesis of Few-Layered Graphene Sheets on A Large Scale Using Chemical Exfoliation," Carbon, vol. 48, no. 8, pp. 2367-2371, 2010.
[52] L. Zhang, J. Liang, Y. Huang, Y. Ma, Y. Wang, and Y. Chen, "Size-Controlled Synthesis of Graphene Oxide Sheets on A Large Scale Using Chemical Exfoliation," Carbon, vol. 47, no. 14, pp. 3365-3368, 2009.
[53] S. Park and R. S. Ruoff, "Chemical Methods for The Production Of Graphenes," Nature Nanotechnology, vol. 4, no. 4, pp. 217-224, 2009.
[54] S. Stankovich, R. D. Piner, S. T. Nguyen, and R. S. Ruoff, "Synthesis and Exfoliation of Isocyanate-Treated Graphene Oxide Nanoplatelets," Carbon, vol. 44, no. 15, pp. 3342-3347, 2006.
[55] D. Li, M. B. Müller, S. Gilje, R. B. Kaner, and G. G. Wallace, "Processable Aqueous Dispersions of Graphene Nanosheets," Nature nanotechnology, vol. 3, no. 2, pp. 101-105, 2008.
[56] S. Stankovich, "Synthesis of Graphene-Based Nanosheets via Chemical Reduction of Exfoliated Graphite Oxide," Carbon, vol. 45, no. 7, pp. 1558-1565, 2007.
[57] V. C. Tung, M. J. Allen, Y. Yang, and R. B. Kaner, "High-Throughput Solution Processing of Large-Scale Graphene," Nature Nanotechnology, vol. 4, no. 1, pp. 25-29, 2009.
[58] A. B. Bourlinos, D. Gournis, D. Petridis, T. Szabó, A. Szeri, and I. Dékány, "Graphite Oxide: Chemical Reduction to Graphite and Surface Modification with Primary Aliphatic Amines and Amino Acids," Langmuir, vol. 19, no. 15, pp. 6050-6055, 2003.
[59] X. Fan, "Deoxygenation of Exfoliated Graphite Oxide Under Alkaline Conditions: A Green Route to Graphene Preparation," Advanced Materials, vol. 20, no. 23, pp. 4490-4493, 2008.
[60] N. Patil, N. Hargude, and M. A. Patil, "Therotical Study of Different Types of Composite Materials," ICRIEM, pp.190-194, 2016.
[61] A. K. Geim, "Graphene: Status and Prospects," Science, vol. 324, no. 5934, pp. 1530-1534, 2009.
[62] 黄毅、陳永胜, "石墨烯的功能化及其相關應用," 中國科學 B 輯化學, vol. 39, no. 9, pp. 887-896, 2009.
[63] S. Niyogi, E. Bekyarova, M. E. Itkis, J. L. McWilliams, M. A. Hamon, and R. C. Haddon, "Solution Properties of Graphite and Graphene," Journal of the American Chemical Society, vol. 128, no. 24, pp. 7720-7721, 2006.
[64] Q. Su, S. Pang, V. Alijani, C. Li, X. Feng, and K. Müllen, "Composites of Graphene with Large Aromatic Molecules," Advanced Materials, vol. 21, no. 31, pp. 3191-3195, 2009.
[65] S. Chen, J. Zhu, X. Wu, Q. Han, and X. Wang, "Graphene Oxide− MnO2 Nanocomposites for Supercapacitors," American Chemical Society Nano, vol. 4, no. 5, pp. 2822-2830, 2010.
[66] S. Wang, M. Tambraparni, J. Qiu, J. Tipton, and D. Dean, "Thermal Expansion of Graphene Composites," Macromolecules, vol. 42, no. 14, pp. 5251-5255, 2009.
[67] L. Ji, "Multilayer Nanoassembly of Sn-Nanopillar Arrays Sandwiched Between Graphene Layers for High-Capacity Lithium Storage," Energy & Environmental Science, vol. 4, no. 9, p. 3611, 2011.
[68] H. A. Becerril, J. Mao, Z. Liu, R. M. Stoltenberg, Z. Bao, and Y. Chen, "Evaluation of Solution-Processed Reduced Graphene Oxide Films As Transparent Conductors," American Chemical Society Nano, vol. 2, no. 3, pp. 463-470, 2008.
[69] J. D. Fowler, M. J. Allen, V. C. Tung, Y. Yang, R. B. Kaner, and B. H. Weiller, "Practical Chemical Sensors From Chemically Derived Graphene," American Chemical Society Nano, vol. 3, no. 2, pp. 301-306, 2009.
[70] 陳文媛、楊邦朝、胡永達, "熱界面材料及其應用," 混合微電子技術, vol. 17, no. 001, pp. 42-53, 2006.
[71] C. Y. Hsieh and S. L. Chung, "High Thermal Conductivity Epoxy Molding Compound Filled with A Combustion Synthesized Aln Powder," Journal of Applied Polymer Science, vol. 102, pp. 4734-4740, 2006.
[72] S. Matsumoto, M. Hino, and T. Kobayashi, "Synthesis of Diamond Films In A RF Induction Thermal Plasma," Applied Physics Letters, vol. 51, pp. 737-739, 1987.
[73] H. Renner, G. Schlamp, K. Zimmermann, W. Weise, P. Tews, K. Dermann, "Silver, Silver Compounds, and Silver Alloys," Ullmann's Encyclopedia of Industrial Chemistry, 1993.
[74] W. L. Peter Ettmayer, "Nitrides," Ullmann's Encyclopedia of Industrial Chemistry, p. 5, 2000.
[75] J H. G. Völz, "Pigments, Inorganic, 1. General," in Ullmann's Encyclopedia of Industrial Chemistry, pp.1-30, 2009.
[76] K. M. Shahil and A. A. Balandin, "Graphene–Multilayer Graphene Nanocomposites as Highly Efficient Thermal Interface Materials," Nano letters, vol. 12, no. 2, pp. 861-867, 2012.
[77] 陳文媛、楊邦朝、胡永達, "熱界面材料及其應用," 混合微電子技術, vol. 17, no. 001, pp. 42-53, 2006.
[78] J. P. Gwinn and R. Webb, "Performance and Testing of Thermal Interface Materials," Microelectronics Journal, vol. 34, no. 3, pp. 215-222, 2003.
[79] H.-T. Fang, "Synthesis of Tin (II or IV) Oxide Coated Multiwall Carbon Nanotubes with Controlled Morphology," The Journal of Physical Chemistry C, vol. 112, no. 15, pp. 5790-5794, 2008.
[80] J. Mittal and K. L. Lin, "Connecting Carbon Nanotubes Using Sn," Journal of Nanoscience and Nanotechnology, vol. 13, no. 8, pp. 5590-5596, 2013.
[81] B. Viswanathan and S. Chokkalingam, "Some Reflections on Mixed Tin and Antimony Oxide Catalysts," Surface Technology, vol. 23, no. 3, pp. 231-244, 1984.
[82] S. Cetinkaya and S. Eroglu, "Thermodynamic Analysis and Reduction of Tin Oxide with Methane," International Journal of Mineral Processing, vol. 110-111, pp. 71-73, 2012.
[83] A. C. Ferrari, "Raman Spectroscopy of Graphene and Graphite: Disorder, Electron–Phonon Coupling, Doping and Nonadiabatic Effects," Solid State Communications, vol. 143, no. 1, pp. 47-57, 2007.
[84] H. Wang, Y. Wang, X. Cao, M. Feng, and G. Lan, "Vibrational Properties of Graphene and Graphene Layers," Journal of Raman Spectroscopy, vol. 40, no. 12, pp. 1791-1796, 2009.
[85] P. Ajayan, "Nanotubes from Carbon," Chemical Reviews, vol. 99, no. 7, pp. 1787-1800, 1999.
[86] 吳娟霞、徐華、張錦, "拉曼光譜在石墨烯結構表徵中的應用," 化學學報, vol. 72, no. 3, pp. 301-318, 2014.
[87] P. G. Jang, K. S. Suh, M. Park, J. K. Kim, W. N. Kim, and H. Gyu Yoon, "Electrical Behavior of Polyurethane Composites with Acid Treatment‐Induced Damage to Multiwalled Carbon Nanotubes," Journal of Applied Polymer Science, vol. 106, no. 1, pp. 110-116, 2007.
[88] I. R. Kabir, "Modelling of Structure-Property Relationship of TMT High Strength Structural Steel Bars," Bangladesh University of Enigineering and Technology (BUET) The degree of Master of Science in Materials and Metallurgical Enginering Thesis, pp.1-81, 2014.
[89] D. Lu and C. Wong, Materials for Advanced Packaging. Germany:Springer, pp.511-537, 2009.
[90] H. O. Pierson, Handbook of Carbon, Graphite, Diamonds and Fullerenes: Processing, Properties and Applications. Noyes Publications, pp.43-58, 2012.
[91] R. A. Serway, Principles of Physics, London: Saunders College Publishing, pp.75-97 ,1998.
[92] V. Q. Nguyen and G. H. Beng, "Thermal Effect on State Estimation in Microgrids," in IPEC, 2010 Conference Proceedings, pp. 848-852, 2010.
[93] Y. Pauleau and P. B. Barna, "Protective Coatings and Thin Films: Synthesis, Characterization and Applications," in Nato Science Partnership Subseries:3, vol.21, pp.229-243, 1996.
[94] Shahil, Khan MF, and Alexander A. Balandin. "Graphene–multilayer graphene nanocomposites as highly efficient thermal interface materials." Nano letters 12.2, pp. 861-867, 2012.
[95] Pan, Xiaoyang, and Zhiguo Yi. "Graphene oxide regulated tin oxide nanostructures: Engineering composition, morphology, band structure, and photocatalytic properties." ACS applied materials & interfaces 7.49, pp.27167-27175, 2015.
[96] mindat.org, 'Graphite', 1993. [Online]. Available: https://www.mindat.org/min-1740.html.