本論文主要分為兩部份，第一部份先探討不同時間成長石墨烯薄膜對場發射的影響，接著轉移不同層數石墨烯於不同結構上做分析，第二部份先探討不同氣體比例成長鑽石薄膜對場發射的影響，接著選取前一節最佳成長鑽石的參數，分別成長於不同結構上做分析，最後將石墨烯結合鑽石，探討其場發射特性。
本論文在四層石墨烯於摻雜矽奈米線結構上得到最低的起始電場1.42V/μm
，石墨烯本身擁有良好的場發射特性，在加上矽奈米線結構摻雜後，因費米能階提升導致功函數下降，使其擁有場發射能力，兩者相互作用，得到最低的起始電場。
而在另一方面，將石墨烯轉移於奈米結構之鑽石上，當四層石墨烯於Ar-N-NDF/Pyramid上得到最低的起始電場1.55V/μm，因鑽石本身的場發能力優越，而石墨烯因金字塔結構造成薄膜破碎，增加了電子發射點，因為兩項優點之結合，使得場發射能力有效提升。

In this study, good electron field emitters based on few graphene coated on wellaligned phosphor-doped Si nanowires were achieved by a simple transfer method and a chemical vapor deposition process. The fewlayer graphene supportedonphosphor-doped Si nanowires andprovides the protruded composite structure, which efficiently enhances the electric field emission.In addition, the use of phosphor-doped Si nanowirespossesses a better field emission ability due to the lift of the Fermi energy level forthe decreased work function.The graphene/phosphor-doped Si nanowireshybrid structure can achieve the lowest turn on value of 1.42 V/μm.

On the other hand, electron field emitter based on diamond/ graphene composite were also investigated. Since diamond films based devices are more reliable in performance because of their unique properties.The novel hetero-structuresof graphene/nanodiamond on pyramid-Si structurewith a marvelous turn on field of 1.55 V/μm was attained.

參考文獻
[1] Matsumoto S., Sato Y., Kamo M., Setaka N., Jpn J Appl Phys, 21, L183(1982)
[2] Matsumoto S., Sato Y., Tsutsumi M., Setaka N., J Mater Sci, 17, 3106(1982) [3] H W Kroto, J R Heath, S C O'Brien, R F Curl, R E Smalley, "C60: Buckminsterfullerene", Nature, 318(No.6042), 162-163 (1985)
[4]Sariciftci NS, Smilowitz L, Heeger AJ, Wudl F.,"Photoinduced electron transfer from a conducting polymer to buckminsterfullerene", Science.Nov 27,258(5087):1474-6 (1992)
[5]Cheng-Kuang Huang, YongxiOu, YaqingBie, Qing Zhao, Dapeng Yu,"Well-aligned graphene arrays for field emission displays", APPLIED PHYSICS, LETTERS 98, 263104 (2011)
[6]IndranilLahiri, Ved Prakash Verma, Wonbong Choi,"An all-graphene based transparent and flexible field emission device", CARBON 49, 1614 – 1619(2011)
[7] http://en.wikipedia.org/wiki/Graphen
[8] A. K. Geim, K. S. Novoselov,"The rise of graphene", Nature Mater, 6, 183 (2007)
[9]朱宏偉,石墨烯:單元子層二維碳晶體-2010年諾貝爾物理獎簡介,自然雜誌,32(6):326~331 (2010)
[10]A. A. Balandin, S. Ghosh, W. Bao, I. Calizo, D. Teweldebrhan, F. Miao, C. N. Lau
, "Superior thermal:conductivity of single-layer graphene".Nano Lett, 8,902-907 (2008)
[11] K.I. Bolotin, K.J. Sikes, Z. Jiang, M. Klima, G. Fudenberg, J. Hone, P. Kim,
H.L. Stormer. "Ultrahigh electron mobility in suspended graphene".Solid State Commun, 146,351-355 (2008)
[12]Keun Soo Kim, Yue Zhao, Houk Jang, Sang Yoon Lee, Jong Min Kim, Kwang S. Kim, Jong-Hyun Ahn, Philip Kim, Jae-Young Choi,ByungHee Hong, "Large-scale pattern growth of graphene films for stretchable transparent electrodes", Nature 457, 706-710 (2009)
[13]R.R. Nair, P. Blake, A.N. Grigorenko, K.S. Novoselov, T. J. Booth, T. Stauber, N.M. R. Peres, A.K. Geim,"Fine Structure Constant Defines Visual Transparency of Graphene", Science,Vol. 320 no. 5881 p. 1308( 2008)
[14]B.Partoens,F.M. Peeters,"From graphene to graphite:electronic structure around the k point", Physics ReviewB,74,075404 (2006)
[15]K.S.Novoselov, A.K.Geim, S.V.Morozov, D.Jiang, Y.Zhang, S.V.Dubonos, I.V.Grigorieva, "A firsovElectric Field Effect in Atomically Thin Carbon Films".Science, 306, 666-669 (2004)
[16]P.Blake,E.W.Hill,A.H.Castro Neto,K.S Novoselov,D.Jiang,R. Yang,T.J.Booth, A.K Geim,"Making graphenevisible", Appl.Phys.Lett, 91, 063124(2007)
[17] C. Berger, Z. Song, T. Li, X. Li, A. Y.Ogbazghi, R.Feng, Z. Dai, A.N.Marchenkov, E.H. Conrad, P.N.First,W. A.de Heer."Ultrathin Epitaxial Graphite:2D Electron Gas Properties and a Route toward Graphene-based Nanoelectronics", J.Phys.Chem.B,108, 19912 (2004)
[18]K.V.Emtsev, A.Bostwick, K. Horn, J.Jobet, G. L. Kellogg, L. Ley, J .L.McChesney, T.Ohta, S. A.Reshanov, J. Rohrl, E. Rotenberg, A. K. Schmid, D.Waldmann, H.B.Weber, T.Seyller. "Towards Wafer-Size Graphene Layers by Atmospheric Pressure Geaphitization of silicon Carbide", Natuer Materials,8,203(2009).
[19]Peter sutter,"Epitaxial Graphene:How Silicon Leaves The Scene",Nature Materials,8,171 (2009)
[20]X.Li,G.Zhang,X.Bai,X.Sun,X.Wang,E. Wang, H.Dai,"Highly conducting graphene sheets and Langmuir-Blodgett films", Nature Nanotech,3, 538-542 (2008)
[21]G.Eda,G.Fanchini, M.Chhowalla, "Large-area ultrathin film of reduced graphene oxide as a transparent and flexible electronic material", Nature Nanotech,3, 270-274 (2008)
[22] Dan Li, Marc B. Müller, Scott Gilje, Richard B. Kaner, Gordon G. Wallace, "Processable aqueous dispersions of graphene nanosheets", Nature Nanotechnology 3, 101 - 105 (2008)
[23] Bae S, Kim H, Lee Y, Xu X, Park JS, Zheng Y, Balakrishnan J, Lei T, Kim HR, Song YI, Kim YJ, Kim KS, Ozyilmaz B, Ahn JH, Hong BH, Iijima S, "Roll-to-roll production of 30-inch graphene films for transparent electrodes",Nat. Nanotechnol. 5, 574 (2010)
[24]P.R.Somani,S.P.Somani,M.Umeno,"Planer nano-graphenes from camphor by CVD",Chemical Physics Letters,430, 56-59 (2006)
[25]Q.Yu, J. Lian, S. Siriponglert, H. Li, Y. P. Chen, S. S. Pei, "Graphene segregated on Ni surfaces and transferred to insulators", Appl.Phys.Lett.93, 113103(2008)
[26]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, R. S. Ruoff, "Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils", Science 324,1312-1314 (2009)
[27] Yu Zhang, Jiale Du, Shuai Tang, Pei Liu, Shaozhi Deng, Jun Chen, Ningsheng Xu,"Optimize the field emission character of a vertical few-layer graphene sheet by manipulating the morphology", Nanotechnology ,23 015202 (6pp) (2012)
[28]S. E. Chen, H. H. Li and J. I. Pang, "The advance of luminescence dating",Journa of Northwest university, vol. 33, no. 2, pp. 209-212(2003)
[29] 余樹楨, 人造鑽石,科學發展1月 409期(2007)
[30]K. E. Spear, J. P. Dismukes,"Synthetic diamond", The Electrochemical Society Series (1993)
[31]S.-T. Lee, Z. Lin, X. Jiang, "CVD diamond films: nucleation and growth", Materials Science and Engineering, pp. 123 (1999)
[32] A. J. Neves, M. H. Nazaré, Properties, "Growth and Applications of Diamond", EMIS Group, Institution of Electrical Engineers (2001)
[33]G. G. P. v. Gorkom, A. M. E. Hoeberechts, "Performance of silicon cold cathodes", J. Vac. Sci. Technol, pp.108 (1986)
[34]F. J. Himpsel, J. A. Knapp, J. A. V. Vechten, D. E. Eastman, "Quantum photoyield pf diamond (111) – A stable negative-affinity surface",PhysRev ,pp. 624 (1979)
[35]Y. C. Chen, X. Y. Zhong, A. R. Konicek, D. S. Grierson, N. H. Tai, I. N. Lin, B. Kabius,J. M. Hiller, A. V. Sumant, R. W. Carpick, and O. Auciello, "Synthesis and characterization of smooth ultra-nanocrystalline diamond films via low pressure bias-enhanced nucleation and growth", APPLIED PHYSICS LETTERS 92, 133113 (2008)
[36]Kane M. O’Donnell , Mark T. Edmonds , JuergenRistein , Anton Tadich , Lars Thomsen ,Qi-Hui Wu , Chris I. Pakes , and Lothar Ley, "Diamond Surfaces with Air-Stable Negative Electron Affinity and Giant Electron Yield Enhancement", Adv. Funct. Mater, 23, 5608–5614 (2013)
[37]I-Nan Lin , Satoshi Koizumi , Joan Yater , and Franz Koeck, "Diamond electron emission", MRS BULLETIN ,vol.39 ( 2014)
[38] Koji Kobashi, "Diamond Films Chemical Vapor Deposition for Oriented and Heteroepitaxial Growth", 290 (2005)
[39] M. Kamo, Y. Sato, "Diamond synthesis from gas phase in microwave plasma", J. Cryst. Growth, vol. 62, pp. 642-644 (1983)
[40] P. K. Bachmann, W. Drawl et al, "Diamond and Diamond-like Materials Synthesis", MRS Symposia Proceeding, vol. EA-15 Pittsburgh, pp. 99-102 (1988)
[41] Debabrata Pradhan and I. Nan Lin, "Grain-Size-DependentDiamond-Nondiamond Composite Films:Characterization and Field-Emission
Properties",APPLIED MATERIALS&INTERFACES, VOL. 1NO. 71444–1450 (2009)
[42] A.R. Kraussa, O. Aucielloa, D.M. Gruena, A. Jayatissaa, A. Sumanta,
J. Tuceka, D.C. Mancinib, N. Moldovanb, A. Erdemirc, D. Ersoyd, M.N. Gardose,H.G. Busmannf, E.M. Meyerg, M.Q. Dingh, "Ultrananocrystalline diamond thin films for MEMS andmoving mechanical assembly devices",Diamond and Related Materials ,10. 1952-1961(2001)
[43]S.Matusumoto, Y.Sato, M.Kamo, and N.Setaka, "Vapor Deposition of Diamond Particles from Methane",Japanese J.Appl. Phys.Lett,p.1562 (1992)
[44]Suneet Arora, V.D. Vankar,"Field emission characteristics of microcrystalline diamond films:Effect of surface coverage and thickness",Thin Solid Films,p.1963 (2006)
[45]S. Matsumoto, M. Hino, T. Kobayashi, "Synthesis of Diamond Films in a RF induction Thermal Plasma", Appl. Phys. Lett, p.737 (1987)
[46]Tao Wang, Li Xiang,"Deposition of diamond/β-SiC/cobalt silicide composite interlayers to improve adhesion of diamond coating on WC–Co substrates by DC-Plasma Assisted HFCVD", Surface & Coatings Technology, 205 3027–3034 (2011)
[47]D.E. Meyer, R.O. Dillon, J.A. Woolam, "Radio-frequency Plasma Chemical Vapor Deposition Growth of Diamond", J. Vac. Sci. Technol., p.2325 (1989)
[48]S.J. Kim, B.K Jul, Y.H. Lee, B.S. Park, IEEE, p.526 (1996)
[49]G. Fedosenko, J. EngemannU, D. Korzec, "Deposition of diamond-like carbon films by a hollow cathode multi-jet RF plasma system", Surface and Coatings Technology, 133-134, 535-539 (2000)
[50] J.Westwater,D.P.Gosain,S.Tomiya,S.Usui,H.Ruda, "Growth of silicon nanowires via gold/silican vapor-liquid-solid reaction", Journal of Vacuum Science＆Technology B, 15, 554-557 (1997)
[51]A.M.Morales, C.M.Lieber. "A laser ablation method for the synthesis of crystalline semiconductor nanowires".Science,279,208-21 (1998)
[52]K.Peng, J. Zhu. "Morphological selection of electroless metal deposits on silicon in aqueous fluoride solution".ElectrochimicaActa, 49,2563-2568 (2004)
[53]T.Qiu, P.K.Chu. "Self-selective electroless plating: An approach for fabrication of functional 1D",nanomaterials.Materials Science andEngineering:R:Reports, 61, 59-77 (2008)
[54]H.Park,S.Kwon,J.S.Lee,H.J.Jim,S.Yoon, D. Kim,"Improvement on surface texturing of single crystalline silicon for solar cell by saw-damage etching using an acidic solution",Solar Energy Materials and SolarCells, 93, 1773-1778 (2009)
[55]A.K.Chu,J.S.Wang,Z.Y.Tsai, C.K.Lee. "A simple and cost-effective approach for fabricating pyramid on crystalline silicon wafers", Solar Energy Materials and Solar Cell,93, 1276-1280 (2009)
[56]I.Zubel, M.Kramkowska,"The effect of isopropyl alcohol on etching rate and roughness of (100) Si surface etched in KOH and TMAH solutions", Sensors and Actuators a-Physical, 93, 138-147 (2001)
[57]H.Lv,H.Shen,Y.Jiang,C.Gao,H.Zhao,J. Yuan,"Porous-pyramids structures silicon surface with low reflectance over a broad band by electrochemical etching", Applied Surface Science,258,5451-5454(2012).
[58]Y.Cao,A.Liu,H.Li,Y.Liu,F.Qiao,Z.Hu,Y. Sang,"Fabrication of silicon wafer with ultra low reflectance by chemical etching method",Applied Surface Science,257, 7411-7414 (2011)
[59]X.Li,B.K.Tay,P.Miele,A.Brioude,D.Cornu,"Fabrication of silicon pyramid/nanowire binary structure with superhydrophobicity",Applied Surface Science,255, 7147-7152 (2009)
[60]K.Q.Peng,J.J.Hu,Y.J.Yan,Y.Wu,H.Fang,Y.Xu,S.T.Lee,J.ZhuAdv, "Fabrication of single crystalline silicon nanowires by scratching a silicon surface with catalytic metal particles", Funct.Mater, 16, 387 (2006)
[61]X.Feng, X. Qi, J. Li, L. Yang, M.Qiu, J. Yin, F. Lu, J. Zhong,"Preparation, structure and photo-catalytic performances of hybrid Bi2SiO5 modified Si nanowire arrays", Applied Surface Science 257, 5571–5575 (2011)
[62]H.Fang,X.Li,S.Song,Y.Xu, J. Zhu,"Fabrication of slantingly-aligned silicon nanowire arrays for solar cell applications", Nanotechnology,19,255703 (2008)
[63]H.Seidel,L.Csepregi,A.Heuberger,H.BaumgSrtel, "Anisotropic Etching of Crystalline Silicon in Alkaline Solutions", J.Electrochem,37, 3612-3626 (1990)
[64]G.T.A.Kovacs,N.I.Maluf, K.E.Petersen,"Bulk micromachining of silicon", IEEE,86,1536-1551 (1998)
[65]S.M.Sze, "Semiconductor Device Physics and Technoligy",2nd edition,JohnWiley&Sons. Inc.,New York (1981)
[66]J.L.Gole,J.D.Stout,W.L.Rauch,Z.L.Wang. "Direct synthesis of silicon nanowires,silica nanospheresand wire-like nanosphere agglomerates", Applied Physics Letter, 76, 2346 (2000)
[67]K.Peng, J. Zhu,"Morphological selection of electroless metal deposits on silicon in aqueous fluoride solution",ElectrochimicaActa, 49, 2563-2568 (2004)
[68] T. K. Chong, K. J. Weber, K. M. Booker, A. W. Blakers, "Characterization of MAE-Textured NanoporousSilicon for Solar Cells Application: Opticsand Surface Passivation",IEEE JOURNAL OF PHOTOVOLTAICS . p. 1235 - 1242 (2014)
[69]Jihun Oh, Hao-Chih Yuan, Howard M. Branz,"An 18.2%-efficient black-silicon solar cellachieved through control of carrierrecombination in nanostructures",Japanese J.Appl. NATURE NANOTECHNOLOGY. VOL 7 (2012)
[70] X. Li, W. Cai, L. Colombo, R. S. Ruoff,"Evolution of Graphene Growthon Ni and Cu by Carbon Isotope Labeling", Nano.Lett,9, 4268-4272 (2009)
[71] Richard L. McCreery,"Raman Spectroscopy for ChemicalAnalysis",John Wiley and Sons. NY, 1-5(2000)
[72]http://www.doganak.com/index.php?option=com_content&view=category&id=114&Itemid=292&lang=en
[73] http://chemlab.jlu.edu.cn/Guojiajingpinke/wuli/shyjchzhsh/xshexian.htm.
[74]朱宏偉,徐志平,謝丹. 結構、制備方法與性能表徵, (2011)
[75]A. C. Ferrari, J. C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri, S. Piscanec, D. Jiang, K. S. Novoselov, S. Roth, and A. K. Geim, "Raman Spectrum of Graphene and Graphene Layers", Phys. Rev. Lett. 97, 187401 (2006)
[76]W. Wu, Z. Liu, L. A. Jauregui, Q. Yu, R. Pillai, H. Cao, J. Bao, Y. P. Chen, S. S. Pei,"Wafer-scale synthesis of graphene by chemical vapor deposition and its application in hydrogen sensing",Sensors and Actuators B ,150, 296–300 (2010)
[77]C. Kuang,Y.Ou,Y.Bie,Q. Zhao,D. Yu. "Well-aligned garphene arrays for emission displays",Appl.Phys.Lett. 98, 263104 (2011)
[78]Srikrishna Pandey, Padmnabh Rai, ShashikantPatole, FethullahGunes,Gi-Duk Kwon, Ji-BeomYoo, Pavel Nikolaev,Sivaram Arepalli1,"Improved electron field emission from morphologically disorderedmonolayer graphene",Appl. Phys. Lett. 100, 043104 (2012)
[79] K. J. Sankaran, K. Srinivasu, H. C. Chen, C. L. Dong, K. C. Leou, C. Y. Lee,N. H. Tai, and I. N. Lin, "Improvement in plasma illumination properties of ultrananocrystalline diamond films by grain boundary engineering",JOURNAL OF APPLIED PHYSICS 114, 054304 (2013)
[80] Y.K. Liu , P.L. Tso , D. Pradhan, I.N. Lin, M. Clark, Y. Tzeng, "Structural and electrical properties of nanocrystalline diamond(NCD) heavily doped by nitrogen", Diamond & Related Materials 14 2059 – 2063(2005)
[81]YonhuaTzeng, ShoupuYeh, Wei Cheng Fang,Yuehchieh Chu, "Nitrogen-incorporatedultrananocrystalline diamond andmulti-layer-graphene-like hybrid carbonfilms”,Scientific Reports 4, Article number: 4531 (2014)
[82] Rami Reddy Devarapalli, Ranjit V. Kashid, Ashvini B. Deshmukh , Ponchami Sharma , Manash R. Das, Mahendra A. More and Manjusha V. Shelke ,"High efficiency electron field emission from protruded graphene oxide nanosheets supported on sharp silicon nanowires", J. Mater. Chem. C, 1, 5040-5046 (2013)
[83] H. Zanin, P. W. May, M. H. M. O. Hamanaka, and E. J. Corat," Field Emission from Hybrid Diamond-like Carbon and Carbon Nanotube Composite Structures", ACS Appl. Mater. Interfaces, 5, 12238−12243(2013)
[84] H. Zanin, P. W. May, M. H. M. O. Hamanaka, and E. J. Corat," Field Emission from Hybrid Diamond-like Carbon and Carbon Nanotube Composite Structures", ACS Appl. Mater. Interfaces, 5, 12238−12243(2013)
[85] Kamatchi Jothiramalingam Sankaran, Srinivasu Kunuku, Keh-Chyang Leou, Nyan-Hwa Tai, I-Nan Lin," Enhancement of the Electron Field Emission Properties of Ultrananocrystalline Diamond Films via Hydrogen Post-Treatment ", ACS Appl. Mater. Interfaces, 6, 14543−14551 (2015)