本論文主要分為兩個部分。
第一部分是研究利用穿透式電子顯微鏡 (Transmission Electron Microscopy, TEM) 的電子束在四氯金酸 (HAuCl4) 水溶液中合成各種不同大小的金奈米粒子並操控之，以了解電子束操控金奈米粒子的作用原理。實驗結果顯示，電子束操控金奈米粒子的作用力是一個電子束對金奈米粒子距離的函數，且最主要的驅動力是Dielectrophoresis所造成的作用力。電子束吸引金奈米粒子的現象是由於觀測窗口 (observation window，為兩厚度約130 nm的平行氮化矽薄膜且相距5 μm (gap) ) 上的電荷累積，而在金奈米粒子中引發一電偶極。此電偶極感受到觀測窗口內的正電場，並向電場較強的電子束照射位置移動，因此可觀察到電子束吸引金粒子的現象。另一方面，金粒子受到電子束排斥的現象，在某些試片中亦被觀察到。推論這可能是由於電子束照射時讓某些金粒子帶正電，因此在觀測窗口內正電場的影響下向遠離電子束的方向移動。
本研究嘗試去了解利用電子束操縱粒子這個新興奈米科技的原理，期望未來藉由了解此技術的機制，加上電子束的高解析、易操控、臨場或即時觀測的能力，可將其應用到各個不同的奈米粒子操縱技術領域。
本論文第二部分，是研究並嘗試證實利用K-kit來觀測液態與固態間奈米級化學反應的可行性，而選擇銀粒子與四氯金酸水溶液間的置換反應作為目標觀察反應。實驗結果觀察到類似文獻上所提及的金銀置換反應所產生的粒子形貌變化。
除了粒子形貌變化的臨場觀測，本研究也成功地利用X光能量散佈分析儀，對K-kit這種特殊試片載體內的液態試片進行成分分析。實驗結果指出，若將單邊K-kit磨薄到100 μm以下，則可用來偵測激發X光的訊號。因此若可以配合反應時的粒子形貌改變，則反應時不同粒子形貌的成分分佈也可以被記錄。

There are two parts in this thesis.
For the first part, the electron beam (E-beam) of a transmission electron microscopy (TEM) was utilized for in-situ synthesizing and manipulating Au nanoparticles with various sizes in HAuCl4 aqueous solution. From experimental observations, the driving force for E-beam manipulation was found to be a function of particle-to-beam distance, mostly contributed by the force of dielectrophoresis. It was observed that the E-beam can attract the Au nanoparticles in the HAuCl4 solution. This contributes to the dipole generated in the Au nanoparticle, induced by the non-uniform positive potential built inside the observation window. On the other hand, this positive potential would induce the repulsion force between the positively charged observation window and the positively charged Au nanoparticles. Therefore, a repulsion behaviour of the Au particle and E-beam was also observed.
In this study, the mechanism of the manipulation of particles by electron beam was investigated. By understanding the working mechanism, it is expected this emerging nanotechnology could be applied to the applications of particle manipulation with high spatial accuracy and its in-situ real-time observation.
For the second part of this thesis is to demonstrate the feasibility of observing the chemical reaction between solid and liquid at the nanometer scale by utilizing the K-kit. The galvanic replacement reaction between Ag nanoparticles and HAuCl4 aqueous solution was selected as the target reaction for observation. A morphology change of nanoparticles similar to previous reports was observed.
In addition to in-situ monitoring the morphology changes of particles, it is demonstrated that energy-dispersive X-ray spectroscopy (EDX) could be used to analyze the liquid sample in K-kit. From the experimental results, if the film-supporting structure (Si) thickness of one side of K-kit was reduced to 100 μm, then the characteristic X-ray of the liquid sample sealed in K-kit could be detected. Therefore, if the EDX results could be compared with the in-situ observation of morphology change of nanoparticle, then the component distribution of different reaction states could be acquired.

摘要 I
Abstract III
誌謝 V
目錄 VIII
圖示說明 XII
表格說明 XVI
第一部分 電子束金奈米粒子操縱術 1
第一章 緒論 1
第二章 文獻回顧 3
2.1粒子操縱術 3
2.1.1利用掃描探針顯微鏡之粒子操縱術 3
2.1.2光鑷 4
2.1.3聲鑷 5
2.1.4利用電子束之粒子操縱術 6
2.2電子束誘導液態前驅物沉積 8
2.2.1利用電子束微影系統之電子束誘導液態前驅物沉積 8
2.2.2利用穿透式電子顯微鏡之電子束誘導液態前驅物沉積 10
第三章 實驗步驟與儀器簡介 11
3.1 實驗步驟 11
3.1.1試樣載體結構與試片製備 11
3.1.2液態前驅物電子束誘導沉積之步驟 18
3.1.3電子束粒子操縱步驟 20
3.2 分析設備與方法 22
3.2.1 穿透式電子顯微鏡 (Transmission Electron Microscopy) 22
第四章 結果與討論 24
4.1 電子束誘導液態前驅物沉積金粒子 24
4.1.1電子束大小對被還原金奈米粒子形貌的影響 24
4.1.2 生成金奈米粒子所需前驅物體積的理論計算 26
4.1.3 試片在穿透式電子顯微鏡腔體內時間長短對於生成金奈米粒子的影響 29
4.1.4 四氯金酸水溶液濃度對於被還原金奈米粒子的影響 31
4.1.5 聚焦電子束照射時間對於還原出來之金奈米粒子大小的影響 33
4.1.6 利用電子束還原出特殊形狀的金奈米粒子及陣列 35
4.2 聚焦電子束操縱所生成之金粒子實驗結果 39
4.2.1利用電子束操縱所生成金奈米粒子位置的結果 39
4.2.2 不同電子束操縱時間對於電子束可影響範圍之影響 43
4.2.3 金粒子尺寸對於電子束操縱的影響 47
4.3 聚焦電子束移動金粒子的機制探討 49
4.3.1 電子束動量轉移至粒子上所造成的作用力 49
4.3.2 系統內電場對金奈米粒子造成的作用力 50
4.3.3 Dielectrophoresis (DEP)所造成的作用力 52
第五章 結論 55
第六章 未來展望 56
第二部分 利用穿透式電子顯微鏡臨場觀測化學反應 57
第一章 緒論 57
第二章 文獻回顧 58
2.1 臨場化學反應觀測 58
2.2 金銀置換反應 59
2.3 利用金銀置換反應生成金的空心奈米結構 60
第三章 實驗步驟與儀器簡介 61
3.1 實驗步驟 61
3.1.1 試片製備 61
3.1.2 穿透式電子顯微鏡中觀察反應 65
3.2 儀器簡介 67
3.2.1 穿透式電子顯微鏡 (Transmission Electron Microscopy) 67
3.2.2 X光能量散佈分析儀(Energy-dispersive X-ray spectroscopy, EDX) 68
第四章 結果與討論 69
4.1 臨場金銀置換反應觀察 69
4.2 X光能量散射能譜分析 72
4.2.1 在K-kit中的銀奈米粒子 72
4.2.2 在K-kit中的去離子水及銀奈米粒子 74
4.2.3 在K-kit中的四氯金酸水溶液及銀奈米粒子 77
4.3 觀察結果討論 80
第五章 結論 82
第六章 未來與展望 83
參考文獻 84
本研究產出之論文發表 89

[1] C. Baur, A. Bugacov, B. E. Koel, A. Madhukar, N. Montoya, T. R. Ramachandran, et al., "Nanoparticle manipulation by mechanical pushing: underlying phenomena and real-time monitoring," Nanotechnology, vol. 9, pp. 360-364, 1998.

[2] S. Kim, F. Shafiei, D. Ratchford, and X. Li, "Controlled AFM manipulation of small nanoparticles and assembly of hybrid nanostructures," Nanotechnology, vol. 22, 2011.

[3] Z. Liu, Z. Li, G. Wei, Y. Song, L. Wang, and L. Sun, "Manipulation, dissection, and lithography using modified tapping mode atomic force microscope," Microscopy Research and Technique, vol. 69, pp. 998-1004, 2006.

[4] I. W. Lyo and P. Avouris, "Field-induced nanometer-scale to atomic-scale manipulation of silicon surface with the STM," Science, vol. 253, pp. 173-176, 1991.

[5] G. H. Yang, L. Tan, Y. Y. Yang, S. W. Chen, and G. Y. Liu, "Single electron tunneling and manipulation of nanoparticles on surfaces at room temperature," Surface Science, vol. 589, pp. 129-138, 2005.

[6] A. Ashkin, "Acceleration and trapping of particles by radiation pressure," Physical Review Letters, vol. 24, pp. 156-159, 1970.

[7] A. Ashkin and J. M. Dziedzic, "Optical trapping and manipulation of viruses and bacteria," Science, vol. 235, pp. 1517-1520, 1987.

[8] A. Ashkin and J. M. Dziedzic, "Internall cell manipulation using infrared-laser traps," Proceedings of the National Academy of Sciences of the United States of America, vol. 86, pp. 7914-7918, 1989.

[9] A. Ashkin, J. M. Dziedzic, J. E. Bjorkholm, and S. Chu, "Observation of a single-beam gradient gorce optical trap for dielectric particles," Optics Letters, vol. 11, pp. 288-290, 1986.

[10] A. Ashkin, J. M. Dziedzic, and T. Yamane, "Optical trapping and manipulation of single cells using infrared-laser beams," Nature, vol. 330, pp. 769-771, 1987.

[11] C. Campbell, "Surface acoustic wave devices and their signal processing applications," Journal of the Acoustical Society of America, vol. 89, pp. 1479-1480, 1991.

[12] J. Shi, D. Ahmed, X. Mao, S. C. S. Lin, A. Lawit, and T. J. Huang, "Acoustic tweezers: patterning cells and microparticles using standing surface acoustic waves (SSAW)," Lab on a Chip, vol. 9, pp. 2890-2895, 2009.

[13] M. C. Jo and R. Guldiken, "Particle manipulation by phase-shifting of surface acoustic waves," Sensors and Actuators a-Physical, vol. 207, pp. 39-42, 2014.

[14] L. Johansson, J. Enlund, S. Johansson, I. Katardjiev, and V. Yantchev, "Surface acoustic wave induced particle manipulation in a PDMS channel-principle concepts for continuous flow applications," Biomedical Microdevices, vol. 14, pp. 279-289, 2012.

[15] X. Ding, S. C. S. Lin, B. Kiraly, H. Yue, S. Li, I. K. Chiang, et al., "On-chip manipulation of single microparticles, cells, and organisms using surface acoustic waves," Proceedings of the National Academy of Sciences of the United States of America, vol. 109, pp. 11105-11109, 2012.

[16] V. P. Oleshko and J. M. Howe, "Are electron tweezers possible?," Ultramicroscopy, vol. 111, pp. 1599-1606, 2011.

[17] H. Zheng, U. M. Mirsaidov, L. W. Wang, and P. Matsudaira, "Electron beam manipulation of nanoparticles," Nano Letters, vol. 12, pp. 5644-5648, 2012.

[18] P. E. Batson, A. Reyes-Coronado, R. G. Barrera, A. Rivacoba, P. M. Echenique, and J. Aizpurua, "Nanoparticle movement: Plasmonic forces and physical constraints," Ultramicroscopy, vol. 123, pp. 50-58, 2012.

[19] N. de Jonge and F. M. Ross, "Electron microscopy of specimens in liquid," Nature Nanotechnology, vol. 6, pp. 695-704, 2011.

[20] H. Zheng, "Using molecular tweezers to move and image nanoparticles," Nanoscale, vol. 5, pp. 4070-4078, 2013 2013.

[21] E. U. Donev and J. T. Hastings, "Electron-Beam-Induced Deposition of Platinum from a Liquid Precursor," Nano Letters, vol. 9, pp. 2715-2718, 2009.

[22] E. U. Donev and J. T. Hastings, "Liquid-precursor electron-beam-induced deposition of Pt nanostructures: dose, proximity, resolution," Nanotechnology, vol. 20, 2009.

[23] G. Schardein, E. U. Donev, and J. T. Hastings, "Electron-beam-induced deposition of gold from aqueous solutions," Nanotechnology, vol. 22, 2011.

[24] X. Chen, K. W. Noh, J. G. Wen, and S. J. Dillon, "In situ electrochemical wet cell transmission electron microscopy characterization of solid–liquid interactions between Ni and aqueous NiCl2," Acta Materialia, vol. 60, pp. 192-198, 2012.

[25] Y. Liu, X. Chen, K. W. Noh, and S. J. Dillon, "Electron beam induced deposition of silicon nanostructures from a liquid phase precursor," Nanotechnology, vol. 23, 2012.

[26] K. L. Liu, C. C. Wu, Y. J. Huang, H. L. Peng, H. Y. Chang, P. Chang, et al., "Novel microchip for in situ TEM imaging of living organisms and bio-reactions in aqueous conditions," Lab on a Chip, vol. 8, pp. 1915-1921, 2008.

[27] J. Belloni, "Nucleation, growth and properties of nanoclusters studied by radiation chemistry: Application to catalysis," Catalysis Today, vol. 113, pp. 141-156, 2006.

[28] J. Cazaux, "Correlation between ionization radiation-damage and charging effect in transmission electron-microscopy," Ultramicroscopy, vol. 60, pp. 411-425, 1995.

[29] M. J. Williamson, R. M. Tromp, P. M. Vereecken, R. Hull, and F. M. Ross, "Dynamic microscopy of nanoscale cluster growth at the solid-liquid interface," Nature Materials, vol. 2, pp. 532-536, 2003.

[30] H. M. Zheng, R. K. Smith, Y. W. Jun, C. Kisielowski, U. Dahmen, and A. P. Alivisatos, "Observation of single colloidal platinum nanocrystal growth trajectories," Science, vol. 324, pp. 1309-1312, 2009.

[31] J. E. Evans, K. L. Jungjohann, N. D. Browning, and I. Arslan, "Controlled growth of nanoparticles from solution with In situ liquid transmission electron microscopy," Nano Letters, vol. 11, pp. 2809-2813, 2011.

[32] C. Mueller, M. Harb, J. R. Dwyer, and R. J. D. Miller, "Nanofluidic cells with controlled path length and liquid flow for rapid, high-resolution In situ imaging with electrons," Journal of Physical Chemistry Letters, vol. 4, pp. 2339-2347, 2013.

[33] X. Lu, J. Chen, S. Skrabalak, and Y. Xia, "Galvanic replacement reaction: a simple and powerful route to hollow and porous metal nanostructures," Proceedings of the Institution of Mechanical Engineers, Part N: Journal of Nanoengineering and Nanosystems, vol. 221, pp. 1-16, 2007.

[34] K. A. Willets and R. P. Van Duyne, "Localized surface plasmon resonance spectroscopy and sensing," Annual Review of Physical Chemistry, vol. 58, pp. 267-297, 2007.

[35] H. Ditlbacher, B. Lamprecht, A. Leitner, and F. Aussenegg, "Spectrally coded optical data storage by metal nanoparticles," Optics letters, vol. 25, pp. 563-565, 2000.

[36] P. V. Kamat, "Meeting the clean energy demand: nanostructure architectures for solar energy conversion," The Journal of Physical Chemistry C, vol. 111, pp. 2834-2860, 2007.

[37] Y. Xia, P. Yang, Y. Sun, Y. Wu, B. Mayers, B. Gates, et al., "One‐dimensional nanostructures: synthesis, characterization, and applications," Advanced materials, vol. 15, pp. 353-389, 2003.

[38] Y. Sun, B. Mayers, T. Herricks, and Y. Xia, "Polyol synthesis of uniform silver nanowires: a plausible growth mechanism and the supporting evidence," Nano Letters, vol. 3, pp. 955-960, 2003.

[39] A. Panáček, L. Kvitek, R. Prucek, M. Kolar, R. Vecerova, N. Pizurova, et al., "Silver colloid nanoparticles: synthesis, characterization, and their antibacterial activity," The Journal of Physical Chemistry B, vol. 110, pp. 16248-16253, 2006.

[40] Y. Sun and Y. Xia, "Shape-controlled synthesis of gold and silver nanoparticles," Science, vol. 298, pp. 2176-2179, 2002.

[41] D. Yu and V. W. W. Yam, "Controlled synthesis of monodisperse silver nanocubes in water," Journal of the American Chemical Society, vol. 126, pp. 13200-13201, 2004.

[42] Y. Xiong, I. Washio, J. Chen, H. Cai, Z. Y. Li, and Y. Xia, "Poly (vinyl pyrrolidone): a dual functional reductant and stabilizer for the facile synthesis of noble metal nanoplates in aqueous solutions," Langmuir, vol. 22, pp. 8563-8570, 2006.

[43] I. Pastoriza‐Santos, J. Pérez‐Juste, S. Carregal‐Romero, P. Hervés, and L. M. Liz‐Marzán, "Metallodielectric hollow shells: optical and catalytic properties," Chemistry–An Asian Journal, vol. 1, pp. 730-736, 2006.

[44] H. Liao, C. L. Nehl, and J. H. Hafner, "Biomedical applications of plasmon resonant metal nanoparticles," Nanomedicine, vol.1, pp. 201-208, 2006.

[45] J. Chen, F. Saeki, B. J. Wiley, H. Cang, M. J. Cobb, Z.-Y. Li, et al., "Gold nanocages: bioconjugation and their potential use as optical imaging contrast agents," Nano letters, vol. 5, pp. 473-477, 2005.