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研究生： 潘建淋
Pan, Chien-Lin
論文名稱： 以角解析光電子能譜研究準自由磊晶石墨烯上鉍薄膜之能帶結構
Investigation of the Band Structure of Bismuth Thin Films on Quasi-Free-Standing Epitaxial Graphene via Angle-Resolved Photoemission Spectroscopy
指導教授： 黃榮俊
Huang, Jung-Chun
學位類別： 碩士
Master
系所名稱： 理學院 - 物理學系
Department of Physics
論文出版年： 2026
畢業學年度： 114
語文別： 中文
論文頁數： 104
中文關鍵詞： 磊晶石墨烯 、碳化矽 、鉍 、插層 、角解析光電子能譜
外文關鍵詞： Epitaxial graphene, Silicon carbide, Bismuth, Intercalation, Angle-resolved photoemission spectroscopy
相關次數： 點閱：74  下載：1 
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    • 鉍（Bi）於SiC(0001) 上可排列成蜂巢狀的鉍烯（bismuthene），其自旋軌道耦合所開啟的拓樸能隙遠大於室溫熱能；然而裸露的鉍烯於大氣中迅速氧化，能長期穩定存在的位置僅有石墨烯之下、與SiC 直接接觸的界面。本研究即嘗試以插層將鉍送入磊晶石墨烯與SiC之間。
    本研究以直流加熱熱分解 4H-SiC(0001) 生長磊晶石墨烯，於1160 至 1400 °C 的窗口內可重複獲得單層至多層石墨烯；經原子氫處理後，摻雜由 n-type轉為 p-type，確認已解耦為準自由磊晶石墨烯（QFEG），但將氫分壓提高四倍反而抑制此一轉換。於此基板以分子束磊晶鍍鉍並退火，自長樣品在五種鍍層與退火條件下，低能電子繞射（LEED）均未出現任何鉍相關的新增訊號；截面穿透式電子顯微鏡(TEM)與能量色散X 光譜(EDX)進一步顯示，鉍以厚度約6 nm 的奈米顆粒聚集於石墨烯之上，元素訊號完全侷限於表層，直接證實插層並未發生。
    為排除層數均勻性與劑量兩項因素，另改用以侷限空間昇華法製備的合作樣品，進行漸進累積式的劑量序列，仍未見插層相。累積至較厚的鍍層後，Γ附近出現一組既不屬於石墨烯亦不屬於SiC 的能帶，於費米能下方約0.5 至 1 eV 之間出現疑似能隙；LEED 則呈現環狀訊號，顯示鉍可能已形成結晶相，惟各晶粒的面內方位彼此隨機。綜合以上，在本研究涵蓋的參數範圍內，自氫解耦後的 QFEG 出發鍍鉍並未導致插層，問題可能與製程路徑的安排有關。

    Bismuth on SiC(0001) forms a honeycomb bismuthene layer whose bonding to the silicon dangling bonds opens a topological gap far larger than room-temperature thermal energy. Because bare bismuthene oxidizes rapidly in air, the graphene/SiC interface is the only site at which it can remain stable, and reaching it requires intercalation. Here epitaxial graphene was grown by direct-current heating of 4H-SiC(0001), atomic hydrogen from a thermal gas cracker was used to decouple the carbon buffer layer into quasi-free-standing epitaxial graphene, and bismuth was then deposited by molecular beam epitaxy and annealed. Across five conditions on self-grown samples, low-energy electron diffraction showed no bismuth superstructure, and cross-sectional electron microscopy with elemental analysis located the bismuth entirely above the graphene as a 6 nm layer of nanoscale grains. A collaborator-supplied sample of superior uniformity, examined through incremental dose sequences, gave the same outcome. Intercalation therefore did not occur within the range explored, and the bismuth instead formed azimuthally disordered islands.

    中文摘要 i Summary ii 誌謝 viii 目錄 ix 表目錄 xii 圖目錄 xiii 第一章 緒論 1 1-1 前言 1 1-1-1 能帶理論 1 1-1-2 自旋軌道耦合 4 1-1-3 拓樸絕緣體 6 1-1-4 二維鉍相 8 1-1-5 插層 10 1-2 研究目標 11 第二章 實驗理論與儀器原理 12 2-1 同步輻射光源 12 2-2 角解析光電子能譜（ARPES） 14 2-2-1 光電子能譜術 14 2-2-2 光電發射的三步模型 16 2-2-3 角度解析與能帶重建 20 2-2-4 超高真空系統（UHV） 24 2-3 低能電子繞射（LEED） 26 2-3-1 基本原理 26 2-4 拉曼光譜學 28 2-4-1 拉曼散射機制 28 2-5 穿透式電子顯微鏡（TEM） 29 2-5-1 電子波長與解析度 29 2-5-2 電子束與物質交互作用及影像模式 29 第三章 實驗材料與方法 32 3-1 材料結構 32 3-1-1 石墨烯的介紹 32 3-1-2 SiC 基板結構 33 3-1-3 SiC/graphene 界面結構 35 3-1-4 bismuthene 37 3-2 SiC 上石墨烯的生長原理 37 3-2-1 熱分解機制 37 3-2-2 氫蝕刻與表面形貌 42 3-2-3 緩衝層（Buffer Layer） 43 3-2-4 石墨烯的表面重構 43 3-2-5 準自由態磊晶石墨烯（QFEG） 45 3-3 樣品製備流程 46 3-3-1 化學清洗 47 3-3-2 實驗腔體與加熱設置 47 3-3-3 氫蝕刻 48 3-3-4 石墨烯生長 48 3-3-5 原子氫插層 49 3-3-6 Bi 蒸鍍 51 3-4 樣品與實驗規劃 52 3-4-1 樣品總覽 52 3-4-2 自長 1150 °C 樣品：鍍 Bi 與鍍率標定 53 3-4-3 合作樣品：漸進累積鍍 Bi 53 3-4-4 合作樣品：原子氫劑量對照的厚膜鍍層 54 第四章 實驗結果與討論 55 4-1 自長樣品的石墨烯生長與鍍 Bi 55 4-1-1 生長溫度系列 ARPES 量測結果與分析 55 4-1-2 原子氫插層量測結果與分析 56 4-1-3 鍍 Bi 後 LEED 量測結果與分析 60 4-1-4 鍍 Bi 樣品截面 TEM/EDX 量測結果與分析 63 4-2 合作樣品的鍍 Bi 劑量序列 67 4-2-1 Bi 劑量序列 ARPES 量測結果與分析 68 4-2-2 累積 57 分鐘厚 Bi 鍍層 ARPES 量測結果與分析 74 4-2-3 鍍 Bi 後 LEED 量測結果與分析 76 4-2-4 小結 77 第五章 結論 78 參考文獻 79

    [1] Kassem Alassaad. Addition of Ge to the H-Si-C Chemical System during SiC Epitaxy. Phd thesis, INSA de Lyon, 2014.
    [2] Yoichi Ando. Topological insulator materials. Journal of the Physical Society of Japan, 82(10):102001, 2013.
    [3] John R. Arthur. Molecular beam epitaxy. Surface Science, 500(1-3):189–217, 2002.
    [4] Neil W. Ashcroft and N. David Mermin. Solid State Physics. Holt, Rinehart and Winston, 1976.
    [5] B. Andrei Bernevig, Taylor L. Hughes, and Shou-Cheng Zhang. Quantum spin Hall effect and topological phase transition in HgTe quantum wells. Science, 314(5806):1757–1761, 2006.
    [6] A. H. Castro Neto, F. Guinea, N. M. R. Peres, K. S. Novoselov, and A. K. Geim. The electronic properties of graphene. Reviews of Modern Physics, 81(1):109–162, 2009.
    [7] Mattia Cattelan and Neil A. Fox. A Perspective on the Application of Spatially Resolved ARPES for 2D Materials. Nanomaterials, 8(5):284, 2018.
    [8] Christian Colliex. Seeing and measuring with electrons: Transmission electron microscopy today and tomorrow – an introduction. Comptes Rendus Physique, 15(2-3):101–109, 2014.
    [9] Paul E. Colombo and Scott W. Priddy. Thermal gas cracking source technology. US Patent 5,693,173, 1997. Filed by Chorus Corp. in 1994; reassigned to Veeco Compound Semiconductor Inc. in 2006. Issued Dec. 2, 1997.
    [10] Andrea Damascelli. Probing the electronic structure of complex systems by ARPES. Physica Scripta, T109:61–74, 2004.
    [11] Andrea Damascelli, Zahid Hussain, and Zhi-Xun Shen. Angle-resolved photoemission studies of the cuprate superconductors. Reviews of Modern Physics, 75(2):473–541, 2003.
    [12] R. B. Darling. Vacuum systems lecture notes, EE-527 Micro-Fabrication. Lecture notes, 2015.
    [13] Walt A. de Heer, Claire Berger, Ming Ruan, Mike Sprinkle, Xuebin Li, Yike Hu, Baiqian Zhang, John Hankinson, and Edward Conrad. Large area and structured epitaxial graphene produced by confinement controlled sublimation of silicon carbide. Proceedings of the National Academy of Sciences, 108(41):16900–16905, 2011.
    [14] Jun-Hao Deng. Growth of few-layer graphene on SiC surface and characterization of their electronic structure by angle-resolved photoemission. Master's thesis, National Tsing Hua University, Hsinchu, Taiwan, 2013.
    [15] Osmary Depablos-Rivera, Ana Martínez, and Sandra E. Rodil. Interpretation of the Raman spectra of bismuth oxide thin films presenting different crystallographic phases. Journal of Alloys and Compounds, 853:157245, 2021.
    [16] K. V. Emtsev, A. Bostwick, K. Horn, J. Jobst, G. L. Kellogg, L. Ley, J. L. McChesney, T. Ohta, S. A. Reshanov, J. Röhrl, E. Rotenberg, A. K. Schmid, D. Waldmann, H. B. Weber, and Th. Seyller. Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide. Nature Materials, 8(3):203–207, 2009.
    [17] K. V. Emtsev, F. Speck, Th. Seyller, L. Ley, and J. D. Riley. Interaction, growth, and ordering of epitaxial graphene on SiC{0001} surfaces: A comparative photoelectron spectroscopy study. Physical Review B, 77(15):155303, 2008.
    [18] Andrea C. Ferrari and Denis M. Basko. Raman spectroscopy as a versatile tool for studying the properties of graphene. Nature Nanotechnology, 8(4):235–246, 2013.
    [19] I. Forbeaux, J.-M. Themlin, and J.-M. Debever. Heteroepitaxial graphite on 6H-SiC(0001): Interface formation through conduction-band electronic structure. Physical Review B, 58(24):16396–16406, 1998.
    [20] Liang Fu and C. L. Kane. Topological insulators with inversion symmetry. Physical Review B, 76(4):045302, 2007.
    [21] Lukas Gehrig, Cedric Schmitt, Jonas Erhardt, Bing Liu, Tim Wagner, Martin Kamp, Simon Moser, and Ralph Claessen. Bismuthene under cover: Graphene intercalation of a large gap quantum spin Hall insulator. Advanced Materials, 37:2502412, 2025.
    [22] A. K. Geim and K. S. Novoselov. The rise of graphene. Nature Materials, 6(3):183–191, 2007.
    [23] Justin George and Debes Bhattacharyya. Graphene: An introduction. In Recent Advances in Graphene and Graphene-Based Technologies. IOP Publishing, 2023.
    [24] M. Z. Hasan and C. L. Kane. Colloquium: Topological insulators. Reviews of Modern Physics, 82(4):3045–3067, 2010.
    [25] H. Hertz. Ueber Einen Einfluss Des Ultravioletten Lichtes Auf Die Electrische Entladung. Annalen der Physik, 267(8):983–1000, 1887.
    [26] Tingwei Hu, Xin Hui, Xiaohe Zhang, Xiangtai Liu, Dayan Ma, Ran Wei, Kewei Xu, and Fei Ma. Nanostructured Bi grown on epitaxial graphene/SiC. The Journal of Physical Chemistry Letters, 9(19):5679–5684, 2018.
    [27] Han Huang, Swee Liang Wong, Yuzhan Wang, Jia-Tao Sun, Xingyu Gao, and Andrew Thye Shen Wee. Scanning tunneling microscope and photoemission spectroscopy investigations of bismuth on epitaxial graphene on SiC(0001). The Journal of Physical Chemistry C, 118(43):24995–24999, 2014.
    [28] Sakhawat Hussain. Structural and Optical Characterization of Green-Yellow Light Emitting Devices with High Indium Concentrated (In,Ga)N Quantum Wells. Ph.d. thesis, Université Nice Sophia Antipolis, 2014. HAL Id: tel-01097095.
    [29] Stefan Hüfner. Photoelectron Spectroscopy. Advanced Texts in Physics. Springer Berlin Heidelberg, 2003.
    [30] Anna Isaeva and Michael Ruck. Crystal chemistry and bonding patterns of bismuth-based topological insulators. Inorganic Chemistry, 59(6):3437–3451, 2020.
    [31] F. Jona, J. A. Strozier, and W. S. Yang. Low-energy electron diffraction for surface structure analysis. Reports on Progress in Physics, 45(5):527–585, 1982.
    [32] C. L. Kane and E. J. Mele. Quantum spin Hall effect in graphene. Physical Review Letters, 95(22):226801, 2005.
    [33] Charles Kittel. Introduction to Solid State Physics. Wiley, 8. ed., [repr.] edition, 2005.
    [34] Markus König, Steffen Wiedmann, Christoph Brüne, Andreas Roth, Hartmut Buhmann, Laurens W. Molenkamp, Xiao-Liang Qi, and Shou-Cheng Zhang. Quantum spin Hall insulator state in HgTe quantum wells. Science, 318(5851):766–770, 2007.
    [35] Michiko Kusunoki, Wataru Norimatsu, Jianfeng Bao, Koichi Morita, and Ulrich Starke. Growth and features of epitaxial graphene on SiC. Journal of the Physical Society of Japan, 84(12):121014, 2015.
    [36] Li-Syuan Lu, Alexander Vera, Furkan Turker, Krishnan Mekkanamkulam Ananthanarayanan, Chengye Dong, Maxwell Wetherington, and Joshua A. Robinson. Atomic-scale confinement at the graphene/SiC interface: A platform for novel two-dimensional nanomaterials. Journal of Vacuum Science & Technology A, 44(3), 2026.
    [37] Shuichi Murakami. Quantum spin Hall effect and enhanced magnetic response by spin-orbit coupling. Physical Review Letters, 97(23):236805, 2006.
    [38] National Synchrotron Radiation Research Center. Synchrotron light source. Technical report, National Synchrotron Radiation Research Center, Hsinchu, Taiwan, 2017.
    [39] National Synchrotron Radiation Research Center. TLS 21b1 beamline information. https://tlsbl.nsrrc.org.tw, 2024. NSRRC, Hsinchu, Taiwan.
    [40] Ryo Noguchi. Backgrounds. In Designing Topological Phase of Bismuth Halides and Controlling Rashba Effect in Films Studied by ARPES, Springer Theses, pages 5–30. Springer, 2022.
    [41] Wataru Norimatsu and Michiko Kusunoki. Transitional structures of the interface between graphene and 6H-SiC (0001). Chemical Physics Letters, 468(1–3):52–56, 2009.
    [42] Wataru Norimatsu and Michiko Kusunoki. Epitaxial graphene on SiC{0001}: Advances and perspectives. Physical Chemistry Chemical Physics, 16(8):3501–3511, 2014.
    [43] Wataru Norimatsu and Michiko Kusunoki. Growth of graphene from SiC{0001} surfaces and its mechanisms. Semiconductor Science and Technology, 29(6):064009, 2014.
    [44] Milton Ohring. Materials Science of Thin Films: Deposition and Structure. Academic Press, San Diego, 2 edition, 2002.
    [45] Taisuke Ohta, Aaron Bostwick, J. L. McChesney, Thomas Seyller, Karsten Horn, and Eli Rotenberg. Interlayer interaction and electronic screening in multilayer graphene investigated with angle-resolved photoemission spectroscopy. Physical Review Letters, 98(20):206802, 2007.
    [46] Charles Paillard, Ritwik Mondal, Marco Berritta, Brahim Dkhil, Surendra Singh, Peter M. Oppeneer, and Laurent Bellaiche. New relativistic Hamiltonian: The angular magnetoelectric coupling. In Spintronics IX, volume 9931 of Proceedings of SPIE, page 99312E, 2016.
    [47] Xiao-Liang Qi and Shou-Cheng Zhang. The quantum spin Hall effect and topological insulators. Physics Today, 63(1):33–38, 2010.
    [48] Xiao-Liang Qi and Shou-Cheng Zhang. Topological insulators and superconductors. Reviews of Modern Physics, 83(4):1057–1110, 2011.
    [49] F. Reis, G. Li, L. Dudy, M. Bauernfeind, S. Glass, W. Hanke, R. Thomale, J. Schäfer, and R. Claessen. Bismuthene on a SiC substrate: A candidate for a high-temperature quantum spin Hall material. Science, 357(6348):287–290, 2017.
    [50] Dominic A. Ricci. Photoemission Studies of Interface Effect on Thin Films Properties. PhD thesis, University of Illinois at Urbana-Champaign, 2006.
    [51] C. Riedl, C. Coletti, T. Iwasaki, A. A. Zakharov, and U. Starke. Quasi-Free-Standing Epitaxial Graphene on SiC Obtained by Hydrogen Intercalation. Physical Review Letters, 103(24):246804, 2009.
    [52] C. Riedl, C. Coletti, and U. Starke. Structural and electronic properties of epitaxial graphene on SiC(0001): A review of growth, characterization, transfer doping and hydrogen intercalation. Journal of Physics D: Applied Physics, 43(37):374009, 2010.
    [53] Yuto Sakakibara, Jianfeng Bao, Junji Yuhara, and Iwao Matsuda. Step unbunching phenomenon on 4H-SiC (0001) surface during hydrogen etching. Applied Physics Letters, 123(3):031603, 2023.
    [54] Kongchao Shen, Chenqiang Hua, Zhaofeng Liang, Yao Wang, Haoliang Sun, Jinping Hu, Huan Zhang, Haiyang Li, Zheng Jiang, Han Huang, Peng Wang, Zhe Sun, Erik Wahlström, Yunhao Lu, and Fei Song. Epitaxial growth of free-standing bismuth film on graphene embedded with nontrivial properties. ACS Applied Electronic Materials, 1(9):1817–1824, 2019.
    [55] Jonathan A. Sobota, Yu He, and Zhi-Xun Shen. Angle-resolved photoemission studies of quantum materials. Reviews of Modern Physics, 93(2):025006, 2021.
    [56] Yeongsup Sohn, Sung Won Jung, Fabian Göhler, Woo Jong Shin, Seyeong Cha, Thomas Seyller, and Keun Su Kim. Electronic band structure of Bi-intercalate layers in graphene and SiC(0001). Journal of the Korean Physical Society, 78(2):157–163, 2021.
    [57] U. Starke, J. Bernhardt, J. Schardt, and K. Heinz. SiC SURFACE RECONSTRUCTION: RELEVANCY OF ATOMIC STRUCTURE FOR GROWTH TECHNOLOGY. Surface Review and Letters, 06(06):1129–1141, 1999.
    [58] V. N. Strocov. Intrinsic accuracy in 3-dimensional photoemission band mapping. Journal of Electron Spectroscopy and Related Phenomena, 130(1-3):65–78, 2003.
    [59] Akari Takayama. High-Resolution Spin-Resolved Photoemission Spectrometer and the Rashba Effect in Bismuth Thin Films. Springer Theses. Springer Japan, 2015.
    [60] Niclas Tilgner, Susanne Wolff, Serguei Soubatch, Tien-Lin Lee, Andres David Peña Unigarro, Sibylle Gemming, F. Stefan Tautz, Thomas Seyller, Christian Kumpf, Fabian Göhler, and Philip Schädlich. Reversible switching of the environment-protected quantum spin Hall insulator bismuthene at the graphene/SiC interface. Nature Communications, 16(1):6171, 2025.
    [61] Qian-Hui Wang. Rotational domains and moiré superlattices driven by interfacial interactions in epitaxial WSe₂/Graphene. Master's thesis, National Yang Ming Chiao Tung University, Hsinchu, Taiwan, 2025.
    [62] David B. Williams and C. Barry Carter. Transmission Electron Microscopy: A Textbook for Materials Science. Springer, 2nd ed edition, 2008.
    [63] Roland Winkler. Spin-Orbit Coupling Effects in Two-Dimensional Electron and Hole Systems, volume 191 of Springer Tracts in Modern Physics. Springer, 2003.
    [64] Wolfspeed, Inc. Wolfspeed materials product line card: 4H-SiC substrates. Product datasheet, 2023.
    [65] Gholam Reza Yazdi, Tihomir Iakimov, and Rositsa Yakimova. Epitaxial graphene on SiC: A review of growth and characterization. Crystals, 6(5):53, 2016.
    [66] Haijun Zhang, Chao-Xing Liu, Xiao-Liang Qi, Xi Dai, Zhong Fang, and Shou-Cheng Zhang. Topological insulators in Bi2Se3, Bi2Te3 and Sb2Te3 with a single Dirac cone on the surface. Nature Physics, 5(6):438–442, 2009.

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