鑽石擁有非常高的導熱性和許多優異的材料特性，是非常適合高頻率、高功率以及在惡劣環境下運作的電子設備材料，銅是目前工業界運用非常廣泛的金屬，由於銅與鑽石皆擁有立方晶體結構且銅與鑽石的晶格不匹配率只有1.14%，另外，銅與碳並不會形成碳化物，且銅是目前常被拿來成長石墨烯的材料之一，這些特質使銅成為成長鑽石非常具有淺力的候選材料，所以我們嘗試在銅基板上利用微波電漿系統成長石墨烯的同時也成長鑽石，研究鑽石在銅上成長以及成核之現象也可以讓我們對於鑽石的成長機制有更進一步的理解。
本論文利用微波電漿輔助化學氣相沉積系統在銅基板上成長鑽石，並研究其成核以及成長的特性。在未經過前處理之銅箔上發現成核密度與製程氣體中甲烷的濃度有很大的關係，甲烷濃度提高會提升鑽石的成核密度以及成長速度，但也會使鑽石中非鑽石相的結構比例提高。在銅基板粗糙度的實驗中，我們發現在粗糙度高的銅基板上更容易產生鑽石成核。在基板前處理方面，超音波震盪處理過之銅箔比起未處理之銅箔可以提升成核密度。在鑽石成長方面，我們發現奈米鑽石成長的狀況與基板表面的特性有關，在低濃度甲烷時銅基板表面可能會改變氣體中碳氫分子的比例和種類或是銅原子可能會擴散到鑽石表面當作觸媒，使得在銅基板表面之奈米鑽石成長速度與在矽基板上不同。單晶鑽石在成長的過程中也會受到銅基板表面的特性影響，使得鑽石在成長過程中容易有其他非鑽石相的結構產生而降低整體鑽石品質。

Both copper and diamond have cubic crystal structure, and the lattice mismatch rate between copper and diamond is only 1.14%. In addition, copper and carbon do not form carbides and thus copper is one of the materials that are frequently used to deposit graphene. These characteristics make copper as a very powerful candidate for growing diamonds. Therefore, the aim of the study is to grow diamond on copper substrate while growing graphene. We anticipate that we can understand the mechanism of diamond nucleation further through the study of diamond growth on copper.
In this thesis, microwave plasma-assisted chemical vapor deposition system was used to grow diamond on copper substrate. When it came to gas ratio, we adjusted the ratio of methane and hydrogen to determine the effect of methane concentration. Furthermore, copper substrates with different surface roughness were employed to evaluate their effect on diamond nucleation. On the other hand, copper foil pretreated by ultrasonic agitation was also applied to test its effect on diamond nucleation. To evaluated the effect of substrate characteristic on diamond growth rate and quality, nanodiamonds and single crystal diamonds were placed on different substrates including copper foil, copper foil with graphene, graphite, diamond thin film and silicon wafer. The results suggest that the growth rate and quality of diamonds are affected by substrate characteristic.

[1] S.-T. Lee, Z. Lin, and X. Jiang, "CVD diamond films: nucleation and growth," Materials Science and Engineering: R: Reports, vol. 25, no. 4, pp. 123-154, 1999.
[2] G. Peschel, "Carbon-carbon bonds: hybridization," Obtained online from: http://www. physik. fu-berlin. de/einrichtungen/ag/ag-reich/lehre/Archiv/ss2011/docs/Gina_Peschel-Handout. pdf, published on, vol. 5, no. 5, 2011.
[3] J. Isberg et al., "High carrier mobility in single-crystal plasma-deposited diamond," Science, vol. 297, no. 5587, pp. 1670-1672, 2002.
[4] C. J. Wort et al., "Recent advances in the quality of CVD diamond optical components," in Window and Dome Technologies and Materials VI, 1999, vol. 3705: International Society for Optics and Photonics, pp. 119-128.
[5] C. J. Wort and R. S. Balmer, "Diamond as an electronic material," Materials today, vol. 11, no. 1-2, pp. 22-28, 2008.
[6] F. Maier, M. Riedel, B. Mantel, J. Ristein, and L. Ley, "Origin of surface conductivity in diamond," Physical review letters, vol. 85, no. 16, p. 3472, 2000.
[7] A. R. Oganov, R. J. Hemley, R. M. Hazen, and A. P. Jones, "Structure, bonding, and mineralogy of carbon at extreme conditions," Reviews in Mineralogy and Geochemistry, vol. 75, no. 1, pp. 47-77, 2013.
[8] 人造鑽石的合成及應用, 曾永華, 陳柏穎, 鄭宇明, and 游銘永, 2014. [Online]. Available: https://scitechvista.nat.gov.tw/c/sW2E.htm
[9] S. Nad, Growth and characterization of large, high quality single crystal diamond substrates via microwave plasma assisted chemical vapor deposition. Michigan State University, 2016.
[10] B. Spitsyn, L. Bouilov, and B. Derjaguin, "Vapor growth of diamond on diamond and other surfaces," Journal of Crystal Growth, vol. 52, pp. 219-226, 1981.
[11] T. A. Grotjohn and J. Asmussen, Microwave plasma-assisted diamond film deposition. New York: Marcel Dekker Inc, 2002.
[12] F. Bundy, W. Bassett, M. Weathers, R. Hemley, H. Mao, and A. Goncharov, "The pressure-temperature phase and transformation diagram for carbon; updated through 1994," Carbon, vol. 34, no. 2, pp. 141-153, 1996.
[13] D. K. Ferry, J. R. Barker, and C. Jacobini, Physics of nonlinear transport in semiconductors. Springer Science & Business Media, 2012.
[14] D. Das and R. N. Singh, "A review of nucleation, growth and low temperature synthesis of diamond thin films," International Materials Reviews, vol. 52, no. 1, pp. 29-64, 2007/01/01 2007, doi: 10.1179/174328007X160245.
[15] V. K. Khanna, "Extreme-Temperature and Harsh-Environment Electronics; Physics, technology and applications," Extreme-Temperature and Harsh-Environment Electronics; Physics, technology and applications, by Khanna, Vinod Kumar. ISBN: 978-0-7503-1156-4. IOP ebooks. Bristol, UK: IOP Publishing, 2017, 2017.
[16] P. Bachmann, D. Leers, and D. Wiechert, "Diamond chemical vapour deposition," Le Journal de Physique IV, vol. 2, no. C2, pp. C2-907-C2-913, 1991.
[17] H. Xiao, "Introduction to Semiconductor Manufacturing Technology. 2001," p515-516, vol. 9.
[18] A. Zaitsev, "Handbook of Industrial Diamonds and Diamond Films," Prelas, M., Popovici, G., Bigelow, L., Eds, pp. 227-376, 1997.
[19] O. Auciello and A. V. Sumant, "Status review of the science and technology of ultrananocrystalline diamond (UNCD™) films and application to multifunctional devices," Diamond and related materials, vol. 19, no. 7-9, pp. 699-718, 2010.
[20] V. Ralchenko et al., "Observation of the Ge-vacancy color center in microcrystalline diamond films," Bulletin of the Lebedev Physics Institute, vol. 42, no. 6, pp. 165-168, 2015.
[21] J. E. Butler and A. V. Sumant, "The CVD of nanodiamond materials," Chemical Vapor Deposition, vol. 14, no. 7‐8, pp. 145-160, 2008.
[22] O. A. Williams et al., "Growth, electronic properties and applications of nanodiamond," Diamond and Related Materials, vol. 17, no. 7-10, pp. 1080-1088, 2008.
[23] Z. V. Živcová, O. Frank, S. Drijkoningen, K. Haenen, V. Mortet, and L. Kavan, "n-Type phosphorus-doped nanocrystalline diamond: electrochemical and in situ Raman spectroelectrochemical study," RSC advances, vol. 6, no. 56, pp. 51387-51393, 2016.
[24] B. Shi, Q. Jin, L. Chen, A. S. Woods, A. J. Schultz, and O. Auciello, "Cell growth on different types of ultrananocrystalline diamond thin films," Journal of functional biomaterials, vol. 3, no. 3, pp. 588-600, 2012.
[25] Y. Mitsuda, Y. Kojima, T. Yoshida, and K. Akashi, "The growth of diamond in microwave plasma under low pressure," Journal of materials science, vol. 22, no. 5, pp. 1557-1562, 1987.
[26] D. Das and R. Singh, "A review of nucleation, growth and low temperature synthesis of diamond thin films," International Materials Reviews, vol. 52, no. 1, pp. 29-64, 2007.
[27] P. Ascarelli and S. Fontana, "Dissimilar grit-size dependence of the diamond nucleation density on substrate surface pretreatments," Applied surface science, vol. 64, no. 4, pp. 307-311, 1993.
[28] H. Liu and D. S. Dandy, "Studies on nucleation process in diamond CVD: an overview of recent developments," Diamond and related Materials, vol. 4, no. 10, pp. 1173-1188, 1995.
[29] S. Iijima, Y. Aikawa, and K. Baba, "Growth of diamond particles in chemical vapor deposition," Journal of materials research, vol. 6, no. 7, pp. 1491-1497, 1991.
[30] B. Lux and R. Haubner, "Nucleation and growth of low-pressure diamond," in Diamond and Diamond-like Films and Coatings: Springer, 1991, pp. 579-609.
[31] Z. Feng, K. Komvopoulos, I. Brown, and D. Bogy, "Effect of graphitic carbon films on diamond nucleation by microwave‐plasma‐enhanced chemical‐vapor deposition," Journal of applied physics, vol. 74, no. 4, pp. 2841-2849, 1993.
[32] H. Jeon, C. Wang, A. Hatta, and T. Ito, "Nucleation-enhancing treatment for diamond growth over a large-area using magnetoactive microwave plasma chemical vapor deposition," Journal of Applied Physics, vol. 88, no. 5, pp. 2979-2983, 2000.
[33] I. Endler, A. Leonhardt, H.-J. Scheibe, and R. Born, "Interlayers for diamond deposition on tool materials," Diamond and related materials, vol. 5, no. 3-5, pp. 299-303, 1996.
[34] L. Golunskia et al., "Optimization of Polycrystalline CVD Diamond Seeding with the Use of sp3/sp2 Raman Band Ratio."
[35] M. Varga, T. Ižák, A. Kromka, M. Veselý, K. Hruška, and M. Michalka, "Study of diamond film nucleation by ultrasonic seeding in different solutions," Central European Journal of Physics, vol. 10, no. 1, pp. 218-224, 2012.
[36] S. Yugo, T. Kanai, T. Kimura, and T. Muto, "Generation of diamond nuclei by electric field in plasma chemical vapor deposition," Applied Physics Letters, vol. 58, no. 10, pp. 1036-1038, 1991.
[37] B. Stoner, G.-H. Ma, S. Wolter, and J. Glass, "Characterization of bias-enhanced nucleation of diamond on silicon by invacuo surface analysis and transmission electron microscopy," Physical Review B, vol. 45, no. 19, p. 11067, 1992.
[38] M. Katoh, M. Aoki, and H. Kawarada, "Plasma-enhanced diamond nucleation on Si," Japanese journal of applied physics, vol. 33, no. 2A, p. L194, 1994.
[39] A. Sawabe and T. Inuzuka, "Growth of diamond thin films by electron assisted chemical vapor deposition," Applied physics letters, vol. 46, no. 2, pp. 146-147, 1985.
[40] X. Li, J. Perkins, R. Collazo, R. J. Nemanich, and Z. Sitar, "Investigation of the effect of the total pressure and methane concentration on the growth rate and quality of diamond thin films grown by MPCVD," Diamond and related materials, vol. 15, no. 11-12, pp. 1784-1788, 2006.
[41] X. F. Ding, X. Sun, W. J. Wang, H. M. Zhang, and H. N. Gao, "Effect of methane concentration on the performance of diamond films prepared by MPCVD," in Advanced Materials Research, 2014, vol. 1053: Trans Tech Publ, pp. 402-406.
[42] P. W. May, "Diamond thin films: a 21st-century material," Philosophical Transactions of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences, vol. 358, no. 1766, pp. 473-495, 2000.
[43] J. Gracio, Q. Fan, and J. Madaleno, "Diamond growth by chemical vapour deposition," Journal of Physics D: Applied Physics, vol. 43, no. 37, p. 374017, 2010.
[44] I. Sakaguchi, M. Nishitani-Gamo, K. P. Loh, H. Haneda, and T. Ando, "Homoepitaxial growth and hydrogen incorporation on the chemical vapor deposited (111) diamond," Journal of applied physics, vol. 86, no. 3, pp. 1306-1310, 1999.
[45] O. A. Williams and R. B. Jackman, "High growth rate MWPECVD of single crystal diamond," Diamond and related materials, vol. 13, no. 4-8, pp. 557-560, 2004.
[46] M. Kawarada, K. Kurihara, and K. Sasaki, "Diamond synthesis on a metal substrate," Diamond and Related Materials, vol. 2, no. 5-7, pp. 1083-1089, 1993.
[47] Y. Kato et al., "Formation of epitaxial 3C-SiC layers by microwave plasma-assisted carbonization," Surface and Coatings Technology, vol. 206, no. 5, pp. 990-993, 2011.
[48] W. R. Lambrecht, C. H. Lee, B. Segall, J. C. Angus, Z. Li, and M. Sunkara, "Diamond nucleation by hydrogenation of the edges of graphitic precursors," Nature, vol. 364, no. 6438, pp. 607-610, 1993.
[49] F. Inzoli, D. Dellasega, V. Russo, F. Ghezzi, and M. Passoni, "Early stages of diamond growth on substrates with different carbon diffusivity," Diamond and Related Materials, vol. 80, pp. 69-75, 2017.
[50] H. Dong, S. Wang, J. J. Galligan, and G. M. Swain, "Boron-doped diamond nano/microelectrodes for bio-sensing and in vitro measurements," Frontiers in bioscience (Scholar edition), vol. 3, p. 518, 2011.
[51] M. Hartsell and L. Piano, "Growth of diamond films on copper," Journal of materials research, vol. 9, no. 4, pp. 921-926, 1994.
[52] L. Constant, C. Speisser, and F. Le Normand, "HFCVD diamond growth on Cu (111). Evidence for carbon phase transformations by in situ AES and XPS," Surface Science, vol. 387, no. 1-3, pp. 28-43, 1997.
[53] Q. H. Fan, E. Pereira, and J. Gracio, "Diamond deposition on copper: studies on nucleation, growth, and adhesion behaviours," Journal of Materials Science, vol. 34, no. 6, pp. 1353-1365, 1999.
[54] Y. Muranaka, H. Yamashita, and H. Miyadera, "Worldwide status of low temperature growth of diamond," Diamond and Related Materials, vol. 3, no. 4-6, pp. 313-318, 1994.
[55] M. J. Baker, C. S. Hughes, and K. A. Hollywood, Biophotonics: Vibrational Spectroscopic Diagnostics. Morgan & Claypool Publishers, 2016.