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研究生: 梁紘
Liang, Hong
論文名稱: 光輔助金屬鈀薄膜蝕刻製程在少層硫化物成長研究
Study of Photo-Assisted Palladium Film Etching for Few Layer Sulfide Synthesis
指導教授: 李敏鴻
Lee, Min-Hung
鍾朝安
Jong, Chao-An
口試委員: 李敏鴻 鍾朝安 陳邦旭
口試日期: 2021/06/21
學位類別: 碩士
Master
系所名稱: 光電工程研究所
Graduate Institute of Electro-Optical Engineering
論文出版年: 2021
畢業學年度: 109
語文別: 中文
論文頁數: 65
中文關鍵詞: 鈀薄膜硫化鈀室溫蝕刻甲酸
英文關鍵詞: Palladium thin film, Palladium sulfide, etch, room temperature, formic acid
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202100992
論文種類: 學術論文
相關次數: 點閱:31下載:4
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  • 本論文目的在開發一個金屬鈀的奈米級蝕刻製程,應用在其成長硫化物層數控制技術開發。首先在大氣與室溫環境下,控制溫濕度條件,利用波長 1064 nm的遠紅外線雷射進行照射,透過不同照射功率與照射次數的改變,探討雷射對金屬鈀薄膜的改質情形。其次,利用雷射照射後的金屬鈀薄膜進行甲酸蒸氣反應實驗,在0.25M、80℃下將甲酸汽化、導入反應腔體與試片反應,進行薄膜單次與循環蝕刻實驗,透過原子力顯微鏡(AFM)的表面粗糙度變化與厚度變化觀察以及光電子能譜儀(XPS)的化學鍵結分析,得知蝕刻反應前後的狀況,包含蝕刻率與蝕刻終點等。透過最佳化蝕刻參數,每循環最小蝕刻速率可小於1nm/cycle,且蝕刻過後表面粗糙度約為0.2nm。
    在其硫化物成長的製程開發方面,利用單加熱區管型爐來進行,硫粉跟試片被放在加熱中心的相反方向來調整氣化溫度跟反應濃度。調整試片位置與中央加熱區溫度,透過拉曼光譜分析結果,得知Pd-S在中心溫度750℃、與中心加熱區距離20cm,得到最佳的硫化鈀成長結果。

    In this study, a nano-scale palladium thin film etch process for few layer sulfide synthesis was investigated. Firstly, an illumination of laser beam of wavelength 1064nm was applied on Pd film surface at room temperature with a controlled humidity and reaction pressure (1 atm). By changing the illumination powers and energy density, the modification of surface bonding before and after illumination were examined. Secondly, the illuminated Pd films were treated by evaporated formic acid steam at 80℃. Through the AFM and XPS inspection in film thickness and binding conditions, the Pd film was etched and the etches thickness were proportional to the applied laser powers. The minimum and maximum etch depth of 0.5 nm and 6.5 nm per cycle were achieved when the applied power were 12W and 27W, respectively. A reliable and cyclable etch process had also been demonstrated.
    As to the sulfide synthesis, a single zone tube furnace was used for metal film sulfidation. The sulfur and the etched Pd film were put at opposite direction of heating center for sulfur concentration tuning and process optimization. By changing the shown in the heating temperature, and the sample position, the optimal Pd-S condition Raman spectrum of was obtained. The layered Pd-S structure synthesis would be well controlled in such a two-step sulfurization process.

    Publication I 期刊論文 I 研討會論文 II 中文摘要 IV Abstract V 致謝 VI 目錄 VII 圖目錄 X 表目錄 XIII 第1章 緒論 1 1-1二維材料介紹 2 1-2 石墨烯 (Graphene) 3 1-3 過渡金屬硫化物 (TMDs) 5 第2章 文獻回顧 8 2-1 二硫化鈀 (PdS2 Palladium disulfide) 8 2-2 製備TMDs 10 2-2.1機械剝離法 (Mechanical Exfoliation) 11 2-2.2化學氣相沉積法 (Chemical Vapor Deposition, CVD) 11 2-2.3 二階段硫化法 12 2-3 金屬鈀蝕刻 14 2-3.1 濕式蝕刻金屬鈀 (Wet etching ) 14 2-3.2 乾式蝕刻金屬鈀 (Dry etching ) 14 2-4 原子層蝕刻 (Atomic layer etching, ALE) 16 2-4.1 氧電漿處理與化學蝕刻 18 2-4.2 紫外線處理與化學蝕刻 21 2-5 研究動機 22 第3章 實驗步驟 24 3-1 實驗流程 24 3-2 前驅物製備 25 3-2.1 試片表面處理 25 3-2.2黃光微影製程 26 3-2.3金屬沉積製程 28 3-2.4剝離成形(Lift-off patterning) 29 3-3 光纖雷射輔助化學蝕刻製程 30 3-3.1光纖雷射規格 30 3-3.2光纖雷射製程 31 3-3.3 化學濕蝕刻製程 32 3-4 硫化製程 33 3-5材料分析儀器 35 3-5.1 原子力顯微鏡 (Atomic Force Microscope, AFM) 35 3-5.2 高解析共焦拉曼顯微鏡光譜儀 ( High Resolution Confocal Raman Microscope ) 36 3-5.3 X光光電子能譜儀(X-ray photoelectron spectroscopy, XPS) 37 3-5.4 X光繞射儀(X-ray diffractometer, XRD) 38 第4章 結果與討論 39 4-1 金屬薄膜成長 39 4-1.1 膜厚量測 40 4-1.2 粗糙鍍量測及3D表面形貌 41 4-2 雷射處理製程 43 4-2.1 雷射處理之表面氧化 43 4-2.2 不同功率之氧化比較 44 4-2.3 不同功率之粗糙度比較 46 4-2.4 不同功率與處理次數之結晶度比較 47 4-3 化學蝕刻製程 50 4-3.1 不同雷射功率之蝕刻深度比較 50 4-3.2 不同雷射功率與蝕刻裝置之多循環蝕刻率比較 51 4-3.3 不同蝕刻濃度之蝕刻率比較 55 4-4 硫化製程 56 4-4.1拉曼光譜分析 ( Raman Spectrum ) 56 4-4.2 結構分析 58 第5章 總結與未來工作 60 5-1 總結 60 5-2未來工作 61 參考文獻 62

    [1] F. Schwierz, J. Pezoldt and R. Granzner,“Two-dimensional materials and their prospects in transistor electronics,” Nanoscale, vol. 7, pp. 8261 (2015)
    [2] Ashtami Jayakumar, Anju Surendranath and Mohanan PV, “ 2D Materials for next Generation Healthcare Applications,” International Journal of Pharmaceutics, vol. 551, no. 1–2, pp. 309–321 (2018)
    [3] K. Geim and I. V. Grigorieva, “Van der Waals heterostructures,” Nature, vol. 499, no. 7459, pp. 419 (2013)
    [4] Pere Miró, Martha Audiffreda and Thomas Heine,“ An atlas of two-dimensional materials,” Chemical Society Reviews, vol. 43, pp. 6537-6554 (2014)
    [5] Chaoliang Tan, Xiehong Cao, Xue-Jun Wu, Qiyuan He, Jian Yang, Xiao Zhang, Junze Chen, Wei Zhao, Shikui Han, Gwang-Hyeon Nam, Melinda Sindoro, and Hua Zhang, “Recent Advances in Ultrathin Two-Dimensional Nanomaterials,” Chemical Reviews, vol. 117, no. 9, pp. 6225-6331 (2017)
    [6] C. N. R. Rao, A. K. Sood, K. S. Subrahmanyam and A. Govindaraj, “Graphene: the new two-dimensional nanomaterial” Angewandte Chemie, vol. 48, no. 42, pp. 7752-7777 (2009)
    [7] Pere Miró, Martha Audiffred and Thomas Heine, “An atlas of two-dimensional materials,” Chemical Society Reviews, vol. 43, no. 9, pp. 6537-6554 (2014)
    [8] S. Mouri, Y. Miyauchi, and K. Matsuda, “Tunable photoluminescence of monolayer MoS2 via chemical doping,” Nano letters, vol. 13, no. 12, pp. 5944-5948 (2013)
    [9] R. J. Toh , Z. Sofer , J. Luxa , D. Sedmidubsky and M. Pumera , “3R phase of MoS2 and WS2 outperforms the corresponding 2H phase for hydrogen evolutionChem,” Chemical Communications, vol. 53,pp. 3054-3057 (2017)
    [10] F.P. Novais Antunes, V.S. Vaiss, S.R. Tavares, R.B. Capaz, A.A. Leitão “Van der Waals interactions and the properties of graphite and 2H-, 3R- and 1T-MoS2: a comparative study Comput. Mater,” Computational Materials Science, vol. 152, pp. 146-150 (2018)
    [11] B. Radisavljevic, A. Radenovic, J. Brivio, V. Giacometti and A. Kis, “Single-layer MoS2 transistors,” Nature Nanotechnology, vol. 6, pp. 147-150 (2011)
    [12] Alberto Ciarrocchi, Ahmet Avsar, Dmitry Ovchinnikov and Andras Kis, “Thickness-Modulated Metal-To-Semiconductor Transformation in a Transition Metal Dichalcogenide,” Nature Communications, vol. 9, pp. 919 (2018)
    [13] Mahdi Ghorbani-Asl, Agnieszka Kuc, Pere Miró and Thomas Heine, “A Single-Material Logical Junction Based on 2D Crystal PdS2,” Advanced Materials, vol. 28, no. 5, pp. 853-856 (2016)
    [14] Enrique G. Marin, Damiano Marian, Marta Perucchini, Gianluca Fiori, and Giuseppe Iannaccone, “Lateral Heterostructure Field-Effect Transistors Based on Two-Dimensional Material Stacks with Varying Thickness and Energy Filtering Source,” ACS Nano, vol. 14, no. 2, pp. 1982-1989 (2020)
    [15] Zhiyuan Zeng, Zongyou Yin, Xiao Huang, Hai Li, Qiyuan He, Gang Lu, Freddy Boey, Hua Zhang, “Single-layer semiconducting nanosheets: high-yield preparation and device fabrication,” Angewandte Chemie, vol. 50, no. 47, pp. 11093-11097 (2011)
    [16] FangLiu, “Mechanical exfoliation of large area 2D materials from vdW crystals,” Progress in Surface Science, vol. 96, no. 2, pp. 1100626 (2021)
    [17] Di Wu, Tai Min, Jian Zhou, Chen Li, Guobin Ma, Gaotian Lu, Minggang Xia and Zhengbin Gu, “Effect of substrate symmetry on the dendrite morphology of MoS2 Film synthesized by CVD” Scientific Reports, vol. 7, pp. 15166 (2017)
    [18] R. Bhatt, S. Bhattacharya, R. Basu , A. Singh , U. Deshpande , C. Surger , S. Basu , D.K. Aswal , S.K. Gupta, “Growth of Pd4S, PdS and PdS2 films by controlled sulfurization of sputtered Pd on native oxide of Si,” Thin Solid Films, vol. 539, pp. 41-46 (2013)
    [19] http://www.naipo.com/Portals/1/web_tw/Knowledge_Center/Research_Development/publish-57.htm
    [20] https://www.tsri.org.tw/tw/commonPage.jsp?kindId=E0021
    [21] https://www.tsri.org.tw/tw/commonPage.jsp?kindId=E0028
    [22] https://www.tsri.org.tw/tw/commonPage.jsp?kindId=E0024
    [23] Steven M. George and Younghee Lee, “Prospects for Thermal Atomic Layer Etching Using Sequential, Self-Limiting Fluorination and Ligand-Exchange Reactions,” ACS Nano, vol. 10, no. 5, pp. 4889-4894 (2016)
    [24] C.-A. Jong et al., 18th ALD conference & 5th ALE workshop (2018)
    [25] K.R. Williams, K. Gupta and M. Wasilik, “Etch rates for micromachining processing-part II,” J. Microelectromech, vol. 12, pp. 761-778 (2003)
    [26] D. Y. Li, "Electron work function at grain boundary and the corrosion behavior of nanocrystalline metallic materials", Mater. Res. Soc. Symp. Proc., Vol. 887 (2006)
    [27] Jae Yong Lee, Jae Sang Choi, Doo Hyun Cho, Su Min Hwang and Chee Won Chung, “Dry etching of palladium thin films in high density plasmas of CH3OH/Ar, C2H5OH/Ar, CH4/Ar, and CH4/O2/Ar gas mixtures,” Thin Solid Films, vol. 636, no.31, pp.325-332 (2017)
    [28] Jack Kun-Chieh Chen, Nicholas D. Altieri, and Taeseung Kim, “Directional etch of magnetic and noble metals. I. Role of surface oxidation states,” Journal of Vacuum Science & Technology A, vol. 35, no. 5, pp.304 (2017)
    [29] Jack Kun-Chieh Chen, Nicholas D. Altieri, Taeseung Kim, and Ernest Chen, “Directional etch of magnetic and noble metals. II. Organic chemical vapor etch,” Journal of Vacuum Science & Technology A, vol. 35, no. 5, pp.305 (2017)
    [30] Brennan M. Coffey, Himamshu C. Nallan, James R. Engstrom and John G. Ekerdt, “A Vacuum Ultraviolet-Enhanced Oxidation Mechanism for Pd: Near-Surface Oxidation for Atomic Layer Etching,” ACS Applied Materials & Interfaces, vol. 12, no. 45, pp. 50985-50995 (2020)
    [31] Brennan M. Coffey, Himamshu C. Nallan, James R. Engstrom, Chon Hei Lam and John G. Ekerdt, “Vacuum Ultraviolet-Enhanced Oxidation—A Route to the Atomic Layer Etching of Palladium Metal,” Chemistry of Materials, vol. 32, no. 14, pp. 6035-6042 (2020)
    [32] A. Monshi, M. R. Foroughi and M. R. Monshi, “Modified Scherrer Equation to Estimate More Accurately Nano-Crystallite Size Using XRD,” World Journal of Nano Science and Engineering, vol.2, pp. 154-160 (2012)

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