臺灣博碩士論文加值系統

鑽石薄膜由於其優異的物理及化學特性，被視為極具潛力的場發射陰極材料。它的場發射行為近年被廣泛的研究，從文獻資料可以大致歸納出幾個重要的影響因素。例如鑽石晶粒的大小，晶界的比例，薄膜導電度，鑽石的缺陷結構，表面官能基，表面粗糙度等等。
本研究發現在薄膜成核過程先行添加奈米石墨纖維，將有助於提升鑽石薄膜成長後的場發射性質。這種薄膜的起始電場達到 4.4 V/μm ,且在7 V/μm 的電場下有0.06 mA/cm2 的電流密度。這種薄膜由於石墨的添加而提升了導電性，並且產生缺陷能帶讓電子場發射更加容易。薄膜中石墨與鑽石的連接還可使薄膜功函數降低，進而降低場發射的起始電場。
本研究針對碳嵌入奈米鑽石薄膜的電子場發射行為進行深入探討。先以場發射掃描式電子顯微鏡和原子力顯微鏡觀察鑽石薄膜表面的形貌及粗糙度。用拉曼光譜儀，X光繞射分析儀，X光光電子能譜儀和穿透式電子顯微鏡觀察其結構，再用四點探針和陰極激發光譜儀量測其導電度和發光特性，最後以自組裝二極式場發射系統量測薄膜的場發射性質。
未來可以調整鑽石薄膜在微波電漿輔助化學氣相沈積成長的製程參數，將其性質最佳化，讓它更符合場發射陰極材料實際應用的需求。

Diamond film has attracted immense attention as a field emission material due to its negative electron affinity and robust mechanical and chemical properties. It has been widely investigated. Based on literatures, the critical factors of diamond film field emission are grain size, the structure of grain boundary, conductivity, graphite structure distribution, structural defect density, surface roughness, surface functional groups, etc.
In this work, nano-graphite fiber embedded nano-crystalline diamond films were synthesized, and it’s excellent electron field emission properties were studied. The nano-graphite fiber embedded nano-crystalline diamond film can be turned on at a low field as 4.4 V/μm and attain large field emission current density about 0.06 mA/cm2 at 7 V/μm applied field. The embedment of nano-graphite increased the conductivity of the film, and lowered the work function of nano-crystalline diamond film. The defects in the diamond structure created additional energy levels in the diamond band structure, which induced electron emission at low electric fields.
The morphology and surface roughness of carbon embedded nano-crystalline diamond films were studied by field emission scanning electron microscope (FESEM) and AFM. Raman, XPS, XRD, TEM, CL are used to investigate the microstructure of the films. Conductivity and field emission properties were measured by four point probe and homemade field emission system respectively.
In the future, the parameters of MPECVD grown nano-crystalline diamond film were further optimized to get better field emission cold cathode materials.

摘要 I
ABSTRACT III
第一章 序論 1
1.1 前言 1
1.2 研究動機 2
第二章 文獻回顧 5
2.1 相關材料簡介 5
2.1.1 碳材料簡介 5
2.1.2 鑽石薄膜 9
2.1.3 微波電漿輔助化學氣相沈積鑽石薄膜 11
2.1.4 鑽石薄膜的成核方法 15
2.2 電子場發射 17
2.2.1 電子場發射特性 17
2.2.2 場發射陰極材料 20
第三章 實驗方法與分析 23
3.1 電泳沈積與不同碳材料嵌入成長奈米晶鑽石薄膜 23
3.1.1 電泳法沈積奈米鑽石顆粒層 23
3.1.2 化學氣相沈積非晶型碳層 24
3.1.3 旋轉塗佈石墨烯 25
3.1.4 旋轉塗佈奈米石墨纖維 26
3.1.5 微波電漿輔助化學氣相沈積成長奈米晶鑽石薄膜 26
3.2 旋轉塗佈鑽石混石墨成長奈米晶鑽石薄膜 28
3.2.1 不同鑽石與石墨混合比例成長鑽石薄膜 28
3.2.2 不同鑽石混石墨懸浮液濃度成長鑽石膜場 29
3.3 材料特性分析儀器與工具 30
3.3.1場發射掃描式電子顯微鏡 (FESEM, JEOL JSM-6500F) 30
3.3.2拉曼光譜分析儀 (Raman, Horida HR 800) 31
3.3.3陰極激發光譜分析 (CL, Gatan MonoCL) 32
3.3.4高解析穿透式電子顯微鏡 (HRTEM, JEOL 2100F) 34
3.3.5 X光光電子能譜儀 (XPS, PHI Quantera SXM) 34
3.3.6原子力顯微鏡 (AFM, SPA-300) 34
3.3.7光電子能譜儀 (AC-2) 35
3.3.8四點探針 35
3.3.9同步輻射Ｘ光繞射 36
3.3.10自組裝二極式場發射量測系統 37
第四章 結果與討論 38
4.1 電泳沈積與不同碳材料嵌入之奈米晶鑽石薄膜場發射分析 38
4.2 旋轉塗佈鑽石混石墨懸浮液成長奈米晶鑽石薄膜之場發射分析 45
4.2.1 不同鑽石與石墨混合比例之鑽石薄膜分析 45
4.2.2 不同鑽石混石墨懸浮液濃度成長鑽石膜場發射分析 54
4.3 不同佈晶成核方式與石墨纖維添加之綜合分析 60
4.3.1 AFM 表面粗糙度分析 61
4.3.2 TEM分析 62
4.3.3 X光光電子能譜分析 68
4.3.4 CL激發光譜分析 70
4.3.5 X光繞射分析 72
4.3.6 光電子能譜功函數量測 74
4.3.7 綜合討論及文獻比較 77

第五章 結論 79
REFERENCE 81
致謝 90

[1] Hsieh, C. T. “Field Emitter Materials prepared using thermal evaporation and chemical vapor deposition”. 2008
[2] Zhu, W.; Kochanski, G. P.; Jin, S. SCIENCE. 1998, 20, 282
[3] Zhu, W.; Kochanski, G. P.; Jin, S.; Seibles, L. Journal of Applied Physics. 1995, 78, 2707
[4] Zhu, W.; Kochanski, G. P.; Jin, S.; Seibles, L. Journal of Vacuum Science Technology. B. 1996, 14, 2011
[5] Cheng, H. F.; Chiang, H. Y.; Horng, C. C.; Chen, H. C.; Wang Ｃ. S.; Lin, I. N. Journal of Applied Physics. 2011, 109, 033711
[6] Pierson, H. O. “The element carbon” in Handbook of carbon, graphite, diamond and fullerenes, Noyes publications. 1993, 11-41
[7] May, P. W. “CVD diamond: a new techonology for the future?’. 1995, 19, 101-106
[8] Liu, H.; Daddy, D. S. “Diamond chemical vapol deposition: Nuclear and Early Growth Stages”. New Jersey, Noyes Publications. 1993
[9] Iijima, S. Nature. 1991, 354, 56.
[10] Pierson, H. O. “The fullerene molecules” in Handbook of carbon, graphite, diamond and fullerenes, Noyes publications. 1993, 356-371
[11] 彭國光.“微波電漿化學氣相沈積法之鑽石薄膜的成長和特性研究 ” 國立清華大學材料科學工程系博士論文. 2002
[12] Erlich, E.; Hausel, W. D. "Diamond deposits: origin, exploration, and history of discovery". Littleton, CO, USA : Society for Mining, Metallurgy, and Exploration. 2002
[13] Bridgman, P. W. "Synthetic diamonds". Scientific American. 1955. 193
[14] Angus, J. C.; Will, H. A.; Stanko, W. S. Journal of Applied Physics. 1968, 39, 2915-2922
[15] Krauss, A.R.; Auciello, O.; Gruen, D.M.; Jayatissa, A.; Sumant, A.; Tucek, J.; Mancini, D.C.; Moldovan, N. ; Erdemir, A.; Ersoy, D.; Gardos, M.N.; Busmann, H.G.; Meyer, E.M.; Ding, M.Q. Diamond and Related Materials. 2001, 10, 1952-1961
[16] Cleri, F.; et al. Europhysics Letters. 1999, 46, 671-677
[17] Rennick, C. J.; Smith, A. G.; Smith, J. A.; Wills, J. B.; Orr-Ewing, A. J.; Ashfold, M. N. R.; Mankelevich, Y. A.; Suetin. N. V. Diamond and Related Materials, 2004, 13, 561-568
[18] Yamanouchi, K.; Sakurai, N.; Satoh, T. Ultrasonics Symposium, Montréal, Québec, Canada. 1989, 1, 351-354
[19] Horner, D. A.; Curtiss, L A.; Gruen, D. M. Chemical Physics Letters. 1995, 233, 243-248
[20] Spitsyn, B. V.; Bouilov, L. L.; Derjaguin, B. V. Journal of Crystal Growth. 1981, 52, 219-226
[22] Matzumoto, S.; Sato, Y.; Kamo, M.; Setaka, N. Japanese Journal of Applied Physics 2. 1982, 21, 183-185
[23] Kamo, M.; Sato, Y.; Matzumoto, S.; Setaka, N. Journal of Crystal Growth. 1983, 62, 642-644
[24] Gruen, D. M.; Liu, S.; Krauss, A. R.; Luo, J.; Pan, X. Applied Physics Letters. 1994, 64, 1502-1504
[25] Cleri, F.; et al. Europhysics Letters. 1999, 46, 671-677
[26] Krauss, A. R.; Auciello, O.; Ding, M. Q.; Gruen, D. M.; Huang, Y.; Zhirnov, V. V.; Givargizov, E. I.; Breskin, A.; Chechen, R.; Shefer, E.; Konov, V.; Pimenov, S.; Karabutov, A.; Rakhimov, A.; Suetin, N. Journal of Applied Physics. 2001, 89, 2958-2967
[27] McCauley, T. G.; Gruen, D. M.; Krauss, A. R. Applied Physics Letters. 1998, 73, 1646-1648
[28] Rabeau, J. R.; John, P.; Wilson, J. I. B.; Fan, Y. Journal of Applied Physics. 2004, 96, 6724-6732
[29] Dubrovinskaia, N.; Dubrovinsky, L.; Langenhorst, F.; Jacobsen, S.; Liebske, C. Diamond and Related Materials. 2005, 14, 16-22
[30] Wang, C. S.; Chen, H. C.; Shih, W. C.; Cheng, H. F.; Lin, I. N. Diamond &; Related Materials. 2010, 19, 138–142
[31] Griffin, J.; Ray, P. C. Nanotechnology. 2006, 17, 1225-1229
[32] Brewer, M. A.; Brown, I. G.; Evans, P. J.; Hoffman, A. Applied Physics Letters. 1993, 63, 1631-1633
[33] Ece, M.; Oral, B.; Patscheider, J.; Ernst, K. H. Diamond and Related Materials. 1995, 4, 720-724
[34] Sun, Z.; Shi, X.; Tay, B. K.; Flynn, D.; Wang, X.; Zheng, Z.; Sun, Y. Diamond and Related Materials. 1997, 6, 230-234.
[35] Yugo, S.; Kanai, T.; Kimura, T.; Muto, T. Applied Physics Letters. 1991. 58, 1036-1038
[36] Xiao, X.; Birrell, J.; Gerbi, J. E.; Auciello, O. Carlisle, J. A. Journal of Applied Physics. 2004. 96, 2232-2239
[37] Gomer, R. Field Emission and Field Ionization, Harvard University Press, Cambridge, MA 1961
[38] Fowler, R.H.; Nordheim, L.W. Proc. The Royal Society (London). A.1928, 119, 173-181
[39] Nordheim, L.W. Proc. The Royal Society (London). A. 1928, 121, 626–639.
[40] Nordheim, L.W. Z. Physik. 1929, 30 (7), 177–196.
[41] Burgess, R.E.; Kroemer, H.; Houston, J.M. Physical Review. 1953, 90, 515
[42] Dyke, W.P.; Trolan, J.K. Physical Review. 1953, 89(4), 799-808
[43] Fursey, G.N.; Ptitsyn, V.E.; Krotevich, D.N. Proc. 11th ISDEIV, 1984, 1, 69-71
[44] Krotevich, D.N.; Ptitsyn, V.E.; Fursey, G.N. Zhurnal Tekhnichekoi Fiziki.1985, 55(3), 625-627
[45] Fursey, G.N.; Tolkacheva, I.D. Radiotekhnika I Elekronika. 1963, 8(7), 1210-1221
[46] Fursey, G.N. Impulse field emission from rhenium. Zhurnal Tekhnichekoi Fiziki .1964, 34(7), 1312-1316
[47] Chang,W. O.; Lee, C. G.; Park, B. G. Journal of Vacuum Science &; Technology B. 1998, 16(2), 807-810
[48] Rakhshandaroo, M.R.; Pang, S.W. Journal of Vacuum Science &; Technology B. 1998, 16(2), 765-767.
[49] Jessing, J.R. Journal of Vacuum Science &; Technology B. 1998, 16(2), 777-779
[50] Merkulov, V. I.; Lowndes, D. H.; Baylor,L. R.; Kang, S. Solid-State Electronics. 2001, 45, 949-956
[51] Satyanarayana, B. S.; Hart, A.; Milne, W. I.; Robertson, J. Journal of Applied Physics. 1997, 71, 1430
[52] Tallant, D. R.; Parmeter, J. E.; Siegal, M. P.; Simpson, R. L. Diamond and Related Materials. 1995, 4, 191-199
[53] Amaratunga, G. A. J.; Silva, S. R. P. Applied Physics Letters. 1996, 68, 2529
[54] Veersamy, V. S.; Yuan, J.; Amaratunga, G. A. J.; Milne, W. I.; Gilkes, K. W. R.; Weilner, M.; Brown, L. M. Physical Review B. 1993, 48, 17954
[55] Wang, C.; Garcia, A.; Ingram, D. C.; Lake, M.; Kordesch, M. E. Electronics Letters.1991, 27, 1459
[56] Xu, N. S.; Latham, R. V. Journal of Physics D. 1993, 26, 1776
[57] Liu, J.; Zhirnov, V. V.; Myers, A. F.; Choi, W. B.; Wojak, G. J.; Hren, J. J. in: Proceedings of 1994 Tri-Service / NASA Cathode Workshop, Cleveland, OH, USA. 1994, 99
[57] Chang, T. C. “Growth of Ultrananocrystalline Diamond Films on Silicon and Tungsten Carbide Substrates Using Electrophoresis-deposited Nano-diamond Film as Nucleation Layer”. 國立清華大學材料科學工程碩士論文. 2011
[59] Eda, G.; Unalan, H. E.; Rupesinghe, N.; Amaratunga, G. A. J.; Chhowalla, M. APPLIED PHYSICS LETTERS. 2008, 93, 233502
[60] Zhanga, X.; Weic, S.; Leib, C.; Weib, J.; Lua, B.; Dinga, Y.; Zhu, C. Applied Surface Science 2011, 257, 5185–5189
[61] Sails, S. R.; Gardiner, D. J.; Bowden, M.; Savage, J.; Rodway, D. Diamond and Related Materials.1996, 5, 589-591
[62] Obraztsov, A. N.; Pavlovsky, I. Y.; Volkov, A. P. Journal of Vacuum Science &; Technology B. 1999, 17(2), 674-678
[63] Obraztsov, A. N.; Volkova, A. P.; Boroninc, A. I.; Kosheevc, S. V. Diamond and Related Materials. 2002, 11, 813–818
[64] Li, L. S.; Zhao, X. THE JOURNAL OF CHEMICAL PHYSICS. 2011, 134, 044711
[65] Litovchenko, V. G.; Evtukh, A. A.; Marchenko, R. I.; Klyui, N. I.; Semenovich, V. A. Applied Surface Science. 1997, 111, 213
[66] Llie, A.; Ferrari, A. C.; Yangi, T.; Robertson, J. Applied Physics Letters. 2000, 76, 2627
[67] Chen, K. H.; Wu, J. J.; Chen, L. C.; Wen, C. Y.; Kichambare, P. D.; Tarntair, F. G.; Kuo, P. F.; Chang, S. W.; Chen, Y. F. Diamond and Related Materials. 2000, 9, 1249
[68] Zhu, W.; Bower, C.; Kochanski, G. P.; Jin, S. Diamond and Related Materials. 2001, 10, 1709
[69] Chen, Y. H.; Hu, C. T.; Lin, I. N. Journal of Applied Physics. 1998, 84, 3890
[70] Tarntair, F. G.; Chen, L. C.; Wei, S. L.; Hong, W. K.; Chen, K. H.; Chen, J. C. Journal of Vacuum Science and Technology B. 2000, 18, 1207
[71] Groning, O.; Kuttel, O. M.; Groning, P.; Schlapbach, L. Applied Surface Science. 1997, 111, 135
[72] Huq, S. E.; Prewett, P. D.; She, J. C.; Deng, S. Z.; Xu, N. S. Material Science and Engineering B. 2000, 74, 184
[73] Okano, K.; Koizumi, S.; Silva, S. R. P.; Amaratunga, G. A. J. Nature. 1996, 381, 140
[74] Zhu, W.; Bower, C.; Kochanski, G. P.; Jin, S. Solid-State Electronic. 2001, 45, 921
[75] Kwo, J. L.; Yokoyama, M.; Wang, W. C.; Chuang, F. Y.; Lin, I. N. Diamond and Related Materials. 2000, 9, 1270
[76] Wen, F. Y.; Chen, L. C.; Wu, J. J.; Chen, K. H.; Kuo, P. F.; Chang, C. W.; Chen, Y. F.; Hong, W. K.; Chen, H. C. Applied Physics Letters. 2000, 18, 2630
[77] Hoshi, F.; Tsugawa, K.; Goto, A.; Ishikura, T.; Yamashita, S.; Yumura, S.; Yumura, M.; Hirao, T.; Oura, K.; Koga, Y. Diamond and Related Materials. 2001, 10, 254