本論文是以氬氣、氫氣和甲烷為氣體源，並加入氮氣作為摻雜源。利用微波電漿輔助化學氣相沉積法，並利用成核及成長兩階段之製程，在n-type (111) 矽基板上成長滲氮鑽石薄膜。本論文針對成長之實驗條件壓力，溫度，微波功率，直流偏壓，成長時間及改變氬氣、甲烷、氮氣比例，對於n-type鑽石薄膜成長所造成的影響做一系統研究。實驗的樣品特性經由電子掃瞄顯微鏡(SEM)，X光繞射儀(XRD)，拉曼光譜儀(Raman)及電流-電壓特性量測(I-V)分析。拉曼光譜是分析鑽石薄膜成長品質最有效的工具。結果顯示，以正偏壓輔助成長可提高鑽石薄膜的品質及滲質濃度。由分析結果，推論氮滲質於晶粒界面之sp2結構中。長時間之成長，薄膜晶粒擴大，而sp2界面物減少，導致導電性變小。

In this work, argon, hydrogen and methane are used as gas sources and nitrogen is used as the doping source. Microwave plasma chemical vapor deposition and two-steps deposition processes have been applied to grow the nitrogen-doped diamond thin film on n-type (111) silicon substrate. Systematical experiments are performed to study the dependence of grown process on working pressure, temperature, microwave power, DC bias, the duration of growth time and the flow rates of gas mixture of argon, methane and nitrogen. The nitrogen-doped diamond thin films are examined by SEM, XRD, Raman and I-V. Raman spectroscopy is the most efficient tool for analyzes the quality of diamond thin films growth. The results show that a positive DC bias can enhance the doping concentration and the qualities of diamond thin films. Form the analyzing results, nitrogen is doped in the sp2 structural grain boundaries of crystallites. The longer diamond thin film grown is, the crystallites become larger and the grain boundaries become smaller, that leads to the larger resistivity of the thin films.

中文摘要………………………………………………………………I
Abstract……………………………………………………….…….II
Contents……………………………………………………………..III
Table captions………………………………………………….……...V
Figure captions………………………………………………………..VI
Chapter 1. Introduction…………………………………………………1
1-1Preface……………………………………………………1
1-2 The properties of nitrogen dopant……………………………3
Chapter 2. Growth Mechanisms of CVD diamond………..…….…….6
2-1 Fundamentals of chemical vapor deposition………………….6
2-2 Formation of Plasma……………..……………………………7
2-3 Mechanism of the sp3 bonds formation……………………….8
Chapter 3. Experimentals………………………………………….…...11
3-1 Sample preparation……………………………………………11
3-2 Microwave plasma CVD system………………….…………..12
3-3 Deposition process….………………………………….…..….13
3-3.1 H2 plasma cleaning………………..…………………..….….13
3-3.2 Nucleation…………………………………………….….…..13
3-3.3 Growth of the n-type diamond films………………….……..14
3-4 Characterizations of diamond films………………………14
3-4.1 Scanning Electron Microscope (SEM)……………………….14
3-4.2 X-ray diffraction measurements…………………….…14
3-4.3 Raman spectroscopy.………………………..……….…15
3-4.4 Current-voltage measurements (I-V)……..……..………..17
Chapter 4. Results and Discussions…………………...…………………18
4-1 The effect of pressure on growing nitrogen doped diamond
films…………………………………………………………….18
4-2 The effect of temperature on growing nitrogen doped diamond films…………………………………………………………...…19
4-3 The effect of microwave power on growing nitrogen doped diamond films……………………………………………………21
4-4 The effect of DC bias on growing nitrogen doped diamond
films……………………………..………………………..…...22
4-5 The effect of growth time on nitrogen doped diamond films…24
4-6 The effect of Ar on growing nitrogen doped diamond films………………………………..…………………………….26
4-7 The effect of CH4 on growing nitrogen doped diamond films………………………….………………………………….27
4-8 The effect of N2 on growing nitrogen doped diamond films………………………………….………………………….28
Chapter 5.Summary………………...…………………………………....30
Reference……………………………...…………………………………32



Table Captions

Table 1-1 Main properties of diamond…………..…………………..…36
Table 1-2 The applications of diamond……….…………………..……37
Table 1-3 Comparisons of the properties of different kind diamond
thin films ………….……………..………………….……...38
Table 3-1 The experimental conditions for the growing processes...….39
Table 3-2 The experimental conditions for diamond growth in variation of the gas mixture………………………….………………..42
Table 3-3 Main Raman peaks of diamond………………...…………...44













Figure Captions

Figure 1-1 Coexisted phase of carbon……………..…..……………45
Figure 1-2 Comparison of diamond (111) and graphite (0001)
structure…………………………………………….….…46
Figure 1-3 (a) The crystal structure of diamond
(b) The cubic unit cell of diamond structure………..…....47
Figure 3-1 Schematic diagram of the MWCVD system…………..….48
Figure 3-2 XRD patterns of diamond structure....……………………49
Figure 3-3 Origin of Rayleigh and Raman scattering…………….…..50
Figure 4-1.1 SEM micrographs of sample N01 (a) surface, and (b) cross-section of diamond thin film.…………………..….51
Figure 4-1.2 SEM micrographs of sample N02 (a) surface, and (b) cross-section of diamond thin film.……………………...52
Figure 4-1.3 SEM micrographs of sample N03 (a) surface, and (b) cross-section of diamond thin film..……………..………53
Figure 4-1.4 SEM micrographs of sample N04 (a) surface, and (b) cross-section of diamond thin film..…………..…………54
Figure 4-1.5 XRD spectra of samples N01, N02, N03 and N04 in variation of pressure………………….………………….55
Figure 4-1.6 Raman spectra of samples N01, N02, and N04 in variation
of pressure……………………………….………………56
Figure 4-2.1 SEM micrographs of sample N05 (a) surface, and (b) cross-section of diamond thin film.………...……………57
Figure 4-2.2 SEM micrographs of sample N06 (a) surface, and (b) cross-section of diamond thin film..………………..……58
Figure 4-2.3 SEM micrographs of sample N07 (a) surface, and (b) cross-section of diamond thin film..…………..…………59
Figure 4-2.4 SEM micrographs of sample N08 (a) surface, and (b) cross-section of diamond thin film..…………………..…60
Figure 4-2.5 XRD spectra of samples N02, N05, N06, N07 and N08
in variation of temperature…………….…………………61
Figure 4-2.6 Raman spectra of samples N02, N05, N06, N07 and N08
in variation of temperature…….……….….…..…………62
Figure 4-2.7 I-V measurements of samples N02, N05, N06, N07 and N08 in variation of temperature………………….………63
Figure 4-3.1 SEM micrographs of sample N09 (a) surface, and (b) cross-section of diamond thin film.……………...………64
Figure 4-3.2 SEM micrographs of sample N010 (a) surface, and (b) cross-section of diamond thin film.……..………….……65
Figure 4-3.3 SEM micrographs of sample N11 (a) surface, and (b) cross-section of diamond thin film.………………..…….66
Figure 4-3.4 SEM micrographs of sample N12 (a) surface, and (b) cross-section of diamond thin film.…………...…………67
Figure 4-3.5 XRD spectra of samples N02, N09, N10, N11 and N12
in variation of microwave power………….……………..68
Figure 4-3.6 Raman spectra of samples N02, N09, N10, N11 and N12
in variation of microwave power…..….…………………69
Figure 4-4.1 SEM micrographs of sample N13 (a) surface, and (b) cross-section of diamond thin film.…..…………….……70
Figure 4-4.2 SEM micrographs of sample N14 (a) surface, and (b) cross-section of diamond thin film.……………..……….71
Figure 4-4.3 SEM micrographs of sample N15 (a) surface, and (b) cross-section of diamond thin film.…………….………..72
Figure 4-4.4 SEM micrographs of sample N16 (a) surface, and (b) cross-section of diamond thin film.………...……………73
Figure 4-4.5 XRD spectra of samples N02, N13, N14, N15 and N16
in variation of DC bias…………………………..……….74
Figure 4-4.6 Raman spectra of samples N02, N13, N14, N15 and N16
in variation of DC bias……………….…………………..75
Figure 4-4.7 I-V measurements of samples N02, N13, N14, N15 and N16 in variation of DC bias……………..……………….76
Figure 4-5.1 SEM micrographs of sample N17 (a) surface, and (b) cross-section of diamond thin film.……………………...77
Figure 4-5.2 SEM micrographs of sample N18 (a) surface, and (b) cross-section of diamond thin film.……………...………78
Figure 4-5.3 SEM micrographs of sample N19 (a) surface, and (b) cross-section of diamond thin film.……………...………79
Figure 4-5.4 SEM micrographs of sample N20 (a) surface, and (b) cross-section of diamond thin film.…………...…………80
Figure 4-5.5 XRD spectra of samples N02, N17, N18, N19 and N20
in variation of grown time……………………………….81
Figure 4-5.6 Raman spectra of samples N02, N17, N18, N19 and N20
in variation of grown time……………………………….82
Figure 4-5.7 I-V measurements of samples N02, N17, N18, N19 and N20 in variation of DC bias…………….……….……….83
Figure 4-5.8 The curve of thickness of samples N02, N18, N19 and N20 in dependence of grown time…………………………….84
Figure 4-6.1 SEM micrographs of sample A01 (a) surface, and (b) cross-section of diamond thin film.………..…………….85
Figure 4-6.2 SEM micrographs of sample A02 (a) surface, and (b) cross-section of diamond thin film.………………….…..86
Figure 4-6.3 SEM micrographs of sample A03 (a) surface, and (b) cross-section of diamond thin film.……..……………….87
Figure 4-6.4 SEM micrographs of sample A04 (a) surface, and (b) cross-section of diamond thin film.………….…………..88
Figure 4-6.5 XRD spectra of samples N02, A01, A02, A03 and A04 in
variation of Ar flow rate……..…………………………..89
Figure 4-6.6 Raman spectra of samples N02, A01, A02, A03 and A04
in variation of Ar flow rate………………..……………..90
Figure 4-7.1 SEM micrographs of sample A05 (a) surface, and (b) cross-section of diamond thin film.………..……………91
Figure 4-7.2 SEM micrographs of sample A06 (a) surface, and (b) cross-section of diamond thin film.………….….………92
Figure 4-7.3 SEM micrographs of sample A07 (a) surface, and (b) cross-section of diamond thin film.….…….……………93
Figure 4-7.4 SEM micrographs of sample A08 (a) surface, and (b) cross-section of diamond thin film.….………………….94
Figure 4-7.5 XRD spectra of samples N02, A05, A06, A07 and A08 in
variation of CH4 flow rate..………………………….….95
Figure 4-7.6 Raman spectra of samples N02, A05, A06, A07 and A08 in variation of CH4 flow rate….…….……………..….…….96
Figure 4-8.1 SEM micrographs of sample A09 (a) surface, and (b) cross-section of diamond thin film.………………….…..97
Figure 4-8.2 SEM micrographs of sample A10 (a) surface, and (b) cross-section of diamond thin film.………….…………..98
Figure 4-8.3 SEM micrographs of sample A11 (a) surface, and (b) cross-section of diamond thin film.……….…………..…99
Figure 4-8.4 SEM micrographs of sample A12 (a) surface, and (b) cross-section of diamond thin film.………….………....100
Figure 4-8.5 XRD spectra of samples N02, A09, A10, A11 and A12 in
variation of N2 flow rate………….…………………….101
Figure 4-8.6 Raman spectra of samples N02, A09, A10, A11 and A12
in variation of N2 flow rate……………………….…….102

1. Hyunjung Kim, R. Vogelgesang, A. K. Ramdas, and S. Rodriguez, Electronic Raman and infrared spectra of acceptors in isotopically controlled diamonds, Phys. Rev. B, 57, 24 (1998)
2. Robert F. Davis, Diamond Films and Coating, Noyes publications, (1992), page 1-64, chapter 1-2
3. David Saada, Joan Adler, R. Kalish, Computer simulation of damage in diamond due to the ion impact and its annealing, Phys. Rev. B, 59, 10 (1999)
4. Lawrence S. Pan, Don R. Kania, Diamond: electronic properties and applications, Kluwer Academic Publishers, (1995) page1-211 chapter 1-5
5. H. Hofsass, M. Dalmer, M. Restle, and C. Ronning, Substitutional phosphorus doping of diamond by ion implantation, J. Appl. Phys. 81, 15 March 1997
6. 周維華，多晶狀鑽石薄膜電傳導特性分析研究，國立雲林科技大學碩士論文 (2000)
7. Takatoshi Yamada and Atsuhito Sawabe, Satoshi Koizumi, Junji Itoh, Ken Okano, Potential profile between boron doped diamond electron emitter and anode electrode, Appl. Phys. Lett. 76, 10 (2000)
8. A.R. Krauss, 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, Ultranano- crystalline diamond thin films for MEMS and moving mechanical assembly devices, Diamond Relat. Mater. 10, (2001) 1952-1961
9. Peter J. Gielisse, V.I. Ivanov-Omskii, G.Popovici, M. Prelas, Diamond & Diamond-like Films Applications, Technomic publishing Co. Inc, (1996) P283
10. Y. Show, T. Matsukawa, H. Ito, M. Iwase, T. Izumi, The electron emissions from nitrogen doped diamond film (effects of defects), Thin Solid Films 377-378 (2000) 214-216
11. I.T. Han and N. Lee, S. W. Lee, S. H. Kim, D. Jeon, Field emission of nitrogen doped diamond films, J. Vac. Sci. Technol. B 16(4), (1998)
12. K. Larsson, Substitutional n-type doping of diamond, Computational Materials Science , 27 (2003) 23-29
13. B. B. Li, M. C. Tosin, A. C. Peterievitz, and V. Baranauskas, Measurement of the substitutional nitrogen activation energy in diamond films, Appl. Phys. Lett. 73, 6 (1998)
14. R. Samlenski, C. Haug, R. Brenn, C. Wild, R. Locher, P. Koidl, Characterisation and lattice location of nitrogen and boron in homoepitaxial CVD diamond, Diamond Relat. Mater. 5 (1996) 947-951
15. L. H. Robins, L. P. Cook, E. N. Farabaugh, and A. Feldman, Cathodoluminescence of defects in diamond films and particles grown by hot-filament chemical-vapor deposition, Phys. Rev. B39 (1989) 13367
16. D. V. Musale, S. R. Sainkar, S. T. Kshirsagar, Raman photolu- minescence and morphological studies of Si- and N-doped diamond films grown on Si (100) substrate by hot-filament chemical vapor deposition technique, Diamond Relat. Mater. 11 (2002) 75-86
17. Masataka Hasegawa, Tokuyuki Teraji and Satoshi Koizumi, Lattice location of phosphorus in n-type homoepitaxial diamond films grown by chemical vapor deposition, Appl. Phys. Lett. 79, 19 (2001)
18. R. Kalish, C. Uzan-Saguy, and A. Samoiloff, R. Locher and P. Koidl, Doping of polycrystalline diamond by boron ion implantation, Appl. Phys. Lett. 64, 19 (1994)
19. Hugh O. Pierson, Handbook of chemical vapor deposition, Noyes publications, (1992) page 81-122, chapter 4
20. F. K. de Theije, J.J. Schermer, W.J.P. van Enckevort, Effects of nitrogen impurities on the CVD growth of diamond: step bunching in theory and experiment, Diamond Relat. Mater. 9 (2000) 1439-1449
21. M. P. Pai, D. V. Musale, S. T. Kshirsagar, A. Mitra, S. R. Sainkar, Effect of coupling of radio-frequency plasma on the growth of diamond films in a hot filament reactor, Thin Solid Films 322 (1998) 167-176
22. J.A. Smith, K.N. Rosser, H. Yagi, M.I. Wallace, P.W. May, M.N.R. Ashfold, Diamond deposition in a DC-arc Jet CVD system: investigations of the effects of nitrogen addition, Diamond Relat. Mater. 10 (2001) 370-375
23. Yang Wubao, Kong Xiang, Yang Size, Duan Xiaofeng, Lu Fanxiu, Nano-crystalline diamond films prepared by microwave argon plasma vapor deposition on optical glass, Vacuum 68 (2003) 49-55


24. D. Behr, R. Locher, J. Wagner and P. Koldl, Epitaxial overgrowth of 13C diamond films on diamond substrates predamaged by ion implantation, J. Appl. Phys. 81, 4 (1997)
25. Thomas G. McCauley, Dieler M. Gruen, and Alan R. Krauss, Temperature dependence of the growth rate for nanocrystalline diamond films deposited from an Ar/CH4 microwave plasma, Appl. Phys. Lett. 73, 12 (1998)
26. Young-Soo Han, Yoon-Kee Kim, Jai-Young Lee, Effects of argon and oxygen addition to the CH4-H2 feed gas on diamond synthesis by microwave plasma enhanced chemical vapor deposition, Thin Solid Films 310 (1997) 39-46
27. Vitor Baranauskas, Helder J. Ceragioli, Alfredo C. Peterlevitz, Marcelo C. Tosin, Effects of argon dilution of an ethanol/hydrogen gas feed on the growth of diamond by hot-filament chemical vapor deposition, Thin Solid Films 377-378 (2000) 303-308
28. 林敬二，儀器分析，美亞書局 (1997), (chapter 18, page 401-414)
29. J. A.N. Goncalves, G.M. Sandonato, K. Iha, Characterization of boron doped CVD diamond films by Raman spectroscopy and X-ray diffractometry, Diamond Relat. Mater. 11 (2002) 1578-1583