臺灣博碩士論文加值系統

摘　　要
石墨烯(graphene)具有優異的導電性、機械特性、熱傳導性、熱穩定性等。自從2004年單層的石墨烯用膠帶機械剝離法製得之後，石墨烯就已經成為目前最熱門研究的題目之一。但是由於膠帶機械剝離法得到的石墨烯面積太小且生產效率低，無法廣泛利用，因此如何製造石墨烯便成為一個有趣且必要的問題。
本論文主要是利用電化學剝離法(electrochemical exfoliation)將石墨進行脫層成石墨烯薄片。利用電流化學效應將石墨電極剝離石墨烯薄片於電解液中，此電化學剝離法被視為一種簡單、低成本、且快速的石墨烯製備方法。
我們使用不同電解電壓(4 V、8 V、12 V)對石墨進行脫層，電解液是選用十二烷基苯磺酸鈉(SDBS)，該電解液在經過電解過程後無需做任何處理，便可使石墨烯薄片均勻的分散在溶液中，最後使用SEM(scanning electron microscope)探討其形貌，以及量測P L探討低溫和常溫下的光學性質。

Abstract
Graphene has excellent electrical conductivity, mechanical properties, thermal conductivity, thermal stability, etc. Since 2004, single-layer graphene has become one of the most popular research targets via tap mechanical exfoliation. Much effort has been exerted recently into the high-yield production of individual graphene flakes two-dimensional (2D) atom-thick platelets of sp2-hybridized carbon atoms.
This research focuses on using electrochemical exfoliation method to delaminate graphite into graphene flakes. Here, we exfoliated the graphite electrode into graphene flakes in the electrolytic solution by electro chemical effect, this electrochemical method is considered as a simple, low cost and rapid preparation of graphene.
First, we used different electrolysis voltages (4 V, 8 V, 12 V) to exfoliate graphite and used sodium dodecylbenzenesulfonate (SDBS) as the electrolyte. After the electrolysis process, graphene flakes can distributed equally in solution without any treatment. Next, we used SEM to investigate the morphology of graphene and measured photoluminescence (PL) to investigate its unique optical properties.

目次
摘　　要 I
Abstract III
誌謝 V
目次 VII
表次 X
圖次 XI
第一章 緒論 1
1.1研究背景與動機 1
1.2石墨烯的特性 2
1.3論文架構 3
第二章 基礎理論 4
2.1石墨烯簡介 4
2.1.1石墨的結構 4
2.1.2石墨烯的應用 6
2.2石墨烯的製備方法 8
2.2.1機械剝離法 8
2.2.2超音波液相剝離法 9
2.2.3氧化還原法 10
2.2.4碳化矽表面磊晶法 11
2.2.5化學氣相沉積法(CVD) 12
2.2.6電化學剝離法 14
2.3石墨烯檢測 16
2.3.1拉曼訊號光譜儀(Raman spectroscopy) 16
2.3.2拉曼光譜判定石墨烯 18
2.3.3 X射線繞射分析儀(XRD) 21
2.3.4 XRD判定石墨烯 23
2.3.5原子力顯微鏡AFM(Atomic Force Microscopy) 24
第三章 實驗介紹 25
3.1實驗設備 25
3.1.1掃描式電子顯微鏡(Scanning electron microscopy，SEM) 25
3.1.2光激發螢光-光譜測量儀 27
3.1.3紫外光可見光吸收光譜儀 32
3.2實驗步驟 33
3.2.1 材料製備前處理 33
3.2.2 藥品配置 33
3.2.3樣品製備 34
3.2.4樣品乾燥與沉積 34
第四章 實驗結果與討論 35
4.1電化學剝離法製備石墨烯之光激發螢光-光譜量測 35
4.1.1電解電壓4V、8V、12V沉積於SiO2(300nm)/Si之PL量測 37
4.1.2電解電壓4V、8V、12V沉積於Glass之PL量測 39
4.1.3相同電解電壓對沉積於不同基板之PL比較 41
4.1.4同基板對不同電解伏特的比較 47
4.2電化學剝離法製備石墨烯之穿透吸收光譜 51
4.2.1不同電解電壓之紫外、可見光之穿透光譜量測 51
4.2.2不同電解電壓之紫外、可見光之吸收光譜量測 55
4.3電化學剝離法製備石墨烯之掃描式電子顯微鏡(Scanning electron microscopy, SEM)分析 59
4.3.1粉末樣品，SEM分析 61
4.3.2沉積薄膜樣品，SEM分析 66
第五章 結論 70
參考文獻 71

參考文獻
[1]Novoselov K. S., Geim A. K., Morozov S. V., Jiang D., Zhang Y., Dubonos S. V., Grigorieva I. V. and Firsov A. A. Electric Field Effect in Atomically Thin Carbon Films [J]. Science, 306: 666-669.(2004).
[2]Q. F. Sun and X. C. Xie, “Quantum transport through a graphene nanoribbon–superconductor junction” J. Phys.:Condens. Matter, vol.21, pp.344204-1-9.(2009).
[3]D. C. Marcano, D. V. Kosynkin, J. M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev, L. B. Alemany, W. Lu and J. M. Tour,“Improved Synthesis of Graphene Oxide”, ACSNANO, vol.4 , pp.4806-4814. (2010)
[4]C. Berger, Z. Song, X. Li, X. Wu, N. Brown, C. Naud, D. Mayou, T. Li, J. Hass, A. N. Marchenkov, E. H. Conrad, P. N. First and W. A. de Heer, “Electronic Confinement and Coherence in Patterned Epitaxial Graphene”, Science., vol. 312, pp.1191-1196. (2006)
[5]W. A. de Heer, C. Berger, X. Wu , P. N. First, E. H. Conrad, X. Li, T. Li, M. Sprinkle, J. Hass, M. L. Sadowski, M. Potemski and Gerard Martinez, “Epitaxial graphene”, Solid State Commun., vol. 143, pp. 92-100. (2007)
[6]C. Berger, Z. Song, X. Li, X. Wu, N. Brown,D. Maud, C. Naud and W. A. de Heer, “Magnetotransport in high mobility epitaxial graphene”, phys. stat. sol., vol. 204, pp. 1746–1750.( 2007)
[7]J. Hass, W. A. de Heer and E. H. Conrad, “The growth and morphology of epitaxial multilayer graphene”, J. Phys.: Condens. Matter, vol. 20, pp. 1-28. (2008)
[8]X. Li, W. Cai, J. An, S. Kim, J. Nah, D. Yang, R. Piner, A. Velamakanni, I. Jung, E. Tutuc, S. K. Banerjee, L. Colombo and R. S. Ruoff, “Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils”, Science., vol. 324, pp.1312-1314. (2009)
[9]A. N. Obraztsov, A. V. Tyurnina, E. A. Obraztsova, A. A. Zolotukhin, B.Liu, K. C. Chin, A. T. S. Wee, “Raman scattering characterization of CVD graphite films”, Carbon, vol. 46, pp.963–968. (2008)
[10]G. Wang, B. Wanget al., “Highly efficient and large-scale synthesis of graphene by electrolytic exfoliation”,Carbon,47, 3242. (2009).
[11] C. Y. Su, A. Y.Luet al., “High-Quality Thin Graphene Films from Fast Electrochemical Exfoliation”,ACS Nano,5(3), 2332. (2011).
[12]M. A. Pimenta, G. Dresselhaus, M. S. Dresselhaus, L. G. Cancado, A. Jorio and R. Saito, “Studying disorder in graphite-based systems by Raman spectroscopy”, Phys. Chem. Chem. Phys., vol. 9, pp.1276–1291. (2007)
[13]G Placzek. Rayleigh-Streuung und Raman-Effekt. Akademische Verlagsgesellschaft, 1934.
[14]L.M. Malard, M.A. Pimenta, G. Dresselhaus, and M.S. Dresselhaus. Ramanspectroscopy in graphene. Phys. Rep, 473:5187, (2009).
[15]Andrea C. Ferrari. Raman spectroscopy of graphene and graphite: Disorder,electron–phonon coupling, doping and nonadiabatic effects. Solid State Communications, 143:47, (2007).
[16]Ni, Z. H.; Wang, Y. Y.; Yu, T.; You, Y. M.; Shen, Z. X.Reduction of Fermi velocity in folded graphene observedby resonance Raman spectroscopy. Phys. Rev. B,77, 235403.(2008)
[17]Wang, Y. Y.; Ni, Z. H.; Shen, Z. X.; Wang, H. M.; Wu, Y. H.Interference enhancement of Raman signal of graphene. Appl. Phys. Lett. 92, 043121. (2008)
[18]Jens Hofrichter, Bartholoma¨us N. Szafranek, Martin Otto, Tim J. Echtermeyer,Matthias Baus, Anne Majerus, Viktor Geringer, Manfred Ramsteiner, and Heinrich Kurz, “Synthesis of Graphene on Silicon Dioxide by a Solid Carbon Source”, Nano Lett. 10, 36-42. (2010),
[19]Z. H. Ni, H. M. Wang, J. Kasim, H. M. Fan, T. Yu, Y. H. Wu,Y. P. Feng and Z. X. Shen, “Graphene Thickness DeterminationUsing Reflection and Contrast Spectroscopy”, Nano Lett., vol. 7, pp.2758-2763.( 2007)
[20] A. C. Ferrari, “Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects”, Solid State Communications, vol. 143, pp.47-57. (2007)
[21]Rahul Rao, Derek Tishler, Jyoti Katoch, and Masa Ishigami. Multiphononraman scattering in graphene. Phys. Rev .B, 84:113406, (2011)
[22]Joseph Goldstein, Dale Newbury, David Joy, Charles Lyman, Patrick Echlin, Eric Lifshin, Linda Sawyer, and Joseph Michael. Scanning Electron Microscopy and X-ray Microanalysis. Springer.(2003)
[23]林建霖,以有機化學氣象沉積法成長m平面氮化銦鎵/氮化鎵量子井之光學特性，中山大學 碩士論文 (2008)
[24]P. Misra, Optical polarization anisotropy in nonpolar GaN thin films due to crystal symmetry and anisotropic strain, Humboldt-university, PhD thesis (2005)
[25]P. Y. Yu , Fundamentals of Semiconductors (Springer, 2001).
[26]陳俊維,國立台灣大學材料系, 石墨烯氧化物的可調變螢光光譜之研究,研究成果