臺灣博碩士論文加值系統

類鑽碳薄膜有著類似鑽石的性質，結構由sp3鑽石鍵結與sp2石墨鍵結組成的非晶態碳薄膜。有絕的機械性質像硬度高、耐磨性……等，可作為保護性鍍膜。但因穿透率不佳，使其在應用上有困難。而藉由參雜可以改善類鑽碳膜的缺點。
電漿輔助化學氣相沉積法(PECVD)是最常見的類鑽碳薄膜製程，而本研究使用的設備與一般的PECVD不同，稱此為射頻負偏壓磁控電漿輔助化學氣相沉積法，在基板加入射頻負偏壓，可控制負偏壓大小外，能夠有效鍍製類鑽碳薄膜沉積於非導體之基材。在此實驗中，利用拉曼光譜儀(Raman)和光電子能譜儀(XPS)量測分析與驗證類鑽碳薄膜特性。甲烷與六甲基二矽氧烷(hexamethyldisiloxane, HMDSO)作為反應氣體，摻雜Si-O結構於類鑽碳薄膜，透過改變HMDSO的流量控制矽氧化合物在膜中的含量。藉由施加偏壓，可以使純類鑽碳薄膜有更好的硬度，薄膜可以從200V的硬度8.16 GPa，加到400V的負偏壓時硬度可以到14.1 GPa，提升72%。參雜HMDSO 1.2 sccm後，薄膜穿透率可以從未參雜HMDSO的類鑽碳薄膜(60 nm)76.9% 提升至86.8 %。參雜HMDSO 0.9 sccm後，薄膜(60 nm)穿透率78.6 %，硬度8.6 Gpa比原本玻璃基板(6 GPa)提升43 %。

Diamond-like carbon (DLC) thin films which were consisted of sp3 diamond structure and sp2 graphite structure is amorphous thin films. It could be protective coatings because of the excellent mechanical properties. But it limits its application for the high intrinsic compressive stress and poor tansmittance. Incorporation of DLC thin films improve the disadventages，and it could be used extensively.
The common process to coating DLC thin films is plasma enhances chemical vapor deposition (PECVD). There are some differences in my experiment instruments. It was named as magnetron plasma enhanced chemical vapor deposition via radio frequency bias. It could control negative bias independently and effectively deposit on the non-conductive substrate. Analyze by using Raman spectrometer and XPS, and verify the properties of the DLC thin films. The DLC thin films with dopping the Si-O structures were deposited in magnetron plasma enhanced chemical vapor deposition via radio frequency bias from the mixture of methane and hexamethyldisiloxane (HMDSO). According to the literatures, applying the negative bias cause the DLC films higher hardness. The pure DLC films applied on 200V negative bias were 8.16 GPa. However,the pure DLC films applied on 400V negative bias were up to 14.1 GPa and improve 72%. The transparency of the films(60 nm) doping 1.2 sccm HMDSO reaches 86.8 %,the transparency of the pure DLC films was 76.9%. The transparency of the films(60 nm) doping 0.9 sccm HMDSO reaches 78.6 %. The hardness of the films doping 0.9 sccm HMDSO were 8.6 GPa and rise to 43% compared with B270 glass substrate(6 GPa).

摘要 I
Abstract II
致謝 III
總目錄 IV
圖目錄 VI
表目錄 IX
第一章 緒論 1
1-1 引言 1
1-2 研究動機 4
第二章 基礎理論 5
2-1 類鑽碳薄膜之結構與分類 5
2-2 類鑽碳薄膜的成長機制 8
2-3 電漿基本原理 10
2-4 電漿輔助化學氣相沉積法 12
2-5 電漿聚合 12
2-6 奈米壓痕 15
第三章 實驗架設與量測儀器 20
3-1 實驗流程 20
3-2 實驗介紹與步驟 21
3-3 量測儀器介紹 26
拉曼光譜儀(Raman Spectroscopy) 26
表面輪廓測定儀(α-step) 31
X射線光電子能譜儀(X-ray Photoelectron Spectroscopy, XPS) 32
紫外/可見/紅外光分光光譜儀 34
奈米壓痕儀 35
第四章 實驗結果與討論 36
4-1 有無DC power中的射頻負偏壓大小對類鑽碳薄膜的影響 36
4-2 電漿功率對於類鑽碳薄膜的影響 43
4-3 甲烷對於電漿沉膜類鑽碳薄膜之影響 46
4-4 摻雜HMDSO對類鑽膜特性的影響 50
4-5 類鑽碳薄膜厚度不同時，類鑽碳薄膜特性之差異 54
第五章 結論 57
參考文獻 58

[1] S. Aisenberg and R. Chabot, "Ion‐Beam Deposition of Thin Films of Diamondlike Carbon," Journal of Applied Physics, vol.42, pp.2953-2958, 1971.
[2] 余樹貞, 晶體之結構與性質. 台北台灣: 渤海堂文化公司, 1993.
[3] W. D. Kingery, H. K. Bowen, D. R. Uhlmann, and R. Frieser, "Introduction to Ceramics,"Journal of The Electrochemical Society, vol.124, p.152C, March 1, 1977 1977.
[4] C. Z. Wang and K. M. Ho, "Structure, dynamics, and electronic properties of diamondlike amorphous carbon," Physical Review Letters, vol.71, pp.1184-1187, 1993.
[5] A. Grill, "Plasma-deposited diamondlike carbon and related materials," IBM Journal of Research and Development, vol.43, pp.147-162, 1999.
[6] X.-z. Ding, F.-m. Zhang, X.-H. Liu, P. W. Wang, W. G. Durrer, W. Y. Cheung, et al., "Ion beam assisted deposition of diamond-like nanocomposite films in an acetylene atmosphere," Thin Solid Films, vol.346, pp.82-85, 1999.
[7] A. Singh and P. Lavigne, "Deposition of diamond-like carbon films by low energy ion beam and d.c. magnetron sputtering," Surface and Coatings Technology, vol.47, pp.188-200, 1991.
[8] S. Flege, R. Hatada, W. Ensinger, and K. Baba, "Properties of hydrogenated DLC films as prepared by a combined method of plasma source ion implantation and unbalanced magnetron sputtering," Journal of Materials Research, vol.27, pp.845-849, 2011.
[9] P. J. Fallon, V. S. Veerasamy, C. A. Davis, J. Robertson, G. A. J. Amaratunga, W. I. Milne, et al., "Properties of filtered-ion-beam-deposited diamondlike carbon as a function of ion energy," Physical Review B, vol.48, pp.4777-4782, 1993.
[10] D. R. McKenzie, "Tetrahedral bonding in amorphous carbon," Reports on Progress in Physics, vol.59, pp.1611-1664, 1996.
[11] T. Michler, M. Grischke, I. Traus, K. Bewilogua, and H. Dimigen, "Mechanical properties of DLC films prepared by bipolar pulsed DC PACVD," Diamond and Related Materials, vol.7, pp.1333-1337, 1998.
[12] N. Kumar, S. A. Barve, S. S. Chopade, R. Kar, N. Chand, S. Dash, et al., "Scratch resistance and tribological properties of SiOx incorporated diamond-like carbon films deposited by r.f. plasma assisted chemical vapor deposition," Tribology International, vol.84, pp.124-131, 2015.
[13] P. Koidl, C. Wild, B. Dischler, J. Wagner, and M. Ramsteiner, "Plasma Deposition, Properties and Structure of Amorphous Hydrogenated Carbon Films," Materials Science Forum, vol.52-53, pp.41-70, 1990.
[14] A. Vanhulsel, J. P. Celis, E. Dekempeneer, J. Meneve, J. Smeets, and K. Vercammen, "Inductively coupled r.f. plasma assisted chemical vapour deposition of diamond-like carbon coatings," Diamond and Related Materials, vol.8, pp.1193-1197, 1999.
[15] L. Zajikova, "Correlation between SiOx content and properties of DLC:SiOx films prepared by PECVD," Surface and Coatings Technology, vol.174-175, pp.281-285, 2003.
[16] Kim, S. G., et al. "Effect of increasing hardness on Si-containing diamond-like carbon film during tribo-test," Diamond and Related Materials, vol.19, pp. 1017-1020, 2010.
[17] F. Zhao, H. Li, L. Ji, Y. Wang, H. Zhou, and J. Chen, "Ti-DLC films with superior friction performance," Diamond and Related Materials, vol.19, pp.342-349, 2010
[18] Zou, C. W., et al. "Effects of Cr concentrations on the microstructure, hardness, and temperature-dependent tribological properties of Cr-DLC coatings," Applied Surface Science, vol.286, pp.137-141, 2013.
[19] N. Dwivedi and S. Kumar, "Nanoindentation testing on copper/diamond-like carbonbi-layer films," Current Applied Physics, vol.12, pp.247-253, 2012.
[20] L.-Y. Chen and F. Chau-Nan Hong, "Effects of SiOx-incorporation hydrocarbons on the tibological properties of DLC films," Diamond and Related Materials, vol.10, pp.1058-1062, 2001.
[21] T. S. Santra, C. H. Liu, T. K. Bhattacharyya, P. Patel, and T. K. Barik, "Characterization of diamond-like nanocomposite thin films grown by plasma enhanced chemical vapor deposition," Journal of Applied Physics, vol.107, p.124320, 2010.
[22] T. S. Santra, T. K. Bhattacharyya, P. Patel, F. G. Tseng, and T. K. Barik, "Structural and tribological properties of diamond-like nanocomposite thin films," Surface and Coatings Technology, vol.206, pp.228-233, 2011.
[23] 混成軌域. Available:http://highscope.ch.ntu.edu.tw/wordpress/?p=9282
[24] C. Casiraghi, A. C. Ferrari, and J. Robertson, "Raman spectroscopy of hydrogenated amorphous carbons," Physical Review B, vol.72, 2005.
[25] H. S. Nalwa, Handbook of thin film materials: Academic Press, 2002.
[26] Y. Lifshitz, S. R. Kasi, and J. W. Rabalais, "Subplantation model for film growth from hyperthermal species: Application to diamond," Physical Review Letters, vol.62, pp.1290-1293, 1989.
[27] 真空技術與應用.台北台灣:財團法人國家實驗研究院儀器科技研究中心, 2001.
[28] Bewilogua, Klaus, and Dieter Hofmann. "History of diamond-like carbon films—from first experiments to worldwide applications," Surface and Coatings Technology, vol.242, pp.214-225, 2014.
[29] Robertson, John. "The deposition mechanism of diamond-like aC and aC: H," Diamond and Related Materials, vol.3, pp.361-368, 1994.
[30] 魏敬倫, "以反應性射頻磁控濺鍍搭配HMDSO電漿聚合鍍製氧化矽摻碳薄膜阻障層之研究," 光電科學與工程學系, 國立中央大學, 桃園台灣, 2012.
[31] 鄭敬龍, "以電漿聚合鍍製氧化矽摻碳氫薄膜應力之研究," 光電科學與工程學系, 國立中央大學, 桃園台灣, 2015.
[32] 張瑞慶, "奈米壓痕技術與應用," ed: 聖約翰科技大學, 2006.
[33] 丁志華, 管正平, 黃新言, and 戴寶通, "奈米壓痕量測系統簡介," 奈米通訊(NDL), vol.9, pp.4-10, 2002.
[34] Li, Xiaodong, and Bharat Bhushan. "A review of nanoindentation continuous stiffness measurement technique and its applications." Materials characterization, vol.48,p.11-36,2002
[35] Raman spectroscopy. Available:https://en.wikipedia.org/wiki/Raman_spectroscopy
[36] A.C.Ferrari,"Determination of bonding in diamond-like carbon by Raman spectroscopy," Diamond and Related Materials, vol.11, pp.1053-1061, 2002.
[37] A. C. Ferrari and J. Robertson, "Interpretation of Raman spectra of disordered and amorphous carbon," Physical review B, vol.61, p.14095, 2000.
[38] 朱柏豪, "表面輪廓儀的用途," 奈米通訊 (NDL), vol.22, pp.31-33.
[39] X-ray photoelectron sectroscopy. Available: https://en.wikipedia.org/wiki/X-ray_photoelectron_spectroscopy
[40] D. H. Lee, X. M. He, K. C. Walter, M. Nastasi, J. R. Tesmer, M. Tuszewski, et al., "Diamondlike carbon deposition on silicon using radio-frequency inductive plasma of Ar and C[sub 2]H[sub 2] gas mixture in plasma immersion ion deposition," Applied Physics Letters, vol.73, p.2423, 1998.
[41] K. H. Schoenbach, A. El-Habachi, W. Shi, and M.Ciocca, "High-pressure hollow cathode discharges," Plasma Sources Science and Technology, vol.6, p.468, 1997.
[42] Y. Lifshitz, "Pitfalls in amorphous carbon studies," Diamond and Related Materials, vol.12, pp.130-140, 2003.