STM and RHEED Studies of Vanadium Nanoclusters Grown on the θ-Al2O3/NiAl(100)

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：114

、訪客IP：3.143.0.18

姓名

蕭凱仁(Kai-Jen Hsiao) 查詢紙本館藏

畢業系所

物理學系

論文名稱

(STM and RHEED Studies of Vanadium Nanoclusters Grown on the θ-Al2O3/NiAl(100))

相關論文

★ 鐵電型液晶材料光熱相變研究	★ An AFM study of thermal behavior of lipid over layers on mica
★ 利用RHEED、LEED、AES 研究Al2O3在NiAl(100)和Co在Al2O3/NiAl(100)上的幾何結構和生長方式	★ Patterning Co Nanoclusters on Thin Film Al2O3/NiAl(100)
★ Growth of Oxide on NiAl(100) and its Interaction with Au	★ 用原子力顯微鏡在脂質膜上做微影術並且討論其在基板上之動力行為
★ Catalytic properties of Au nanoclusters supported on Al2O3/NiAl (100) surface	★ Atomic Structures and Electro-catalytic Properties of Pt Nanoclusters on Thin Film Al2O3/NiAl(100)
★ Nanowires from Aligned One-dimensional Arrays of Co Nanoclusters on Al2O3 Grown on Vicinal NiAl Surfaces	★ 以掃描穿隧電子顯微鏡及光激發能譜研究奈金屬粒子在氧化鋁薄膜上的成長
★ 在氧化鋁上成長金與白金的和金奈米粒子	★ 以第一原理研究一到二顆金原子在θ型氧化鋁(001)表面上的吸附與擴散行為
★ 甲醇在以thita-三氧化二鋁/鎳鋁合金為基板之奈米黃金粒子上的分解反應-以熱脫附質譜術與傅立葉紅外光譜儀方法之研究	★ 探測θ-Al2O3/NiAl(100)表面之下的結構以及Au-Pt雙金屬顆粒在θ-Al2O3/NiAl(100)表面上的形貌
★ 利用穿隧式電子顯微鏡的探針產生在鎳鋁合金(100)面上的局部氧化反應	★ 利用PES探討吸附物對Au-Pt奈米團簇所引發表面發生重構的現象

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

[檢視]

[下載]

本電子論文使用權限為同意立即開放。
已達開放權限電子全文僅授權使用者為學術研究之目的，進行個人非營利性質之檢索、閱讀、列印。
請遵守中華民國著作權法之相關規定，切勿任意重製、散佈、改作、轉貼、播送，以免觸法。

摘要(中)

在催化過程中的反應性和選擇性可以透過控制金屬奈米團簇的大小來做改變，尺寸效應因此在奈米團簇的催化性質研究中扮演重要角色，為了說明尺寸效應，了解納米團簇的原子結構知識是必要的。目前的工作致力於研究Vanadium (V)金屬奈米團簇生長在Al2O3/NiAl(100)上的形貌與原子結構。我們在超高真空的條件下以掃描穿隧式顯微鏡顯微鏡(Scanning Tunneling Microscope, STM)和高能電子繞射儀(Reflection High Energy Electron Diffraction, RHEED)來研究，主要研究釩奈米團簇在室溫下的成長模式以及加熱對奈米團簇造成的影響。在室溫下形成的V奈米團簇隨著鍍量的增加，奈米團簇的尺寸會成長:直徑從1.56 nm增加到2.07 nm，高度從0.46 nm增加到0.66 nm。在低覆蓋率(< 0.88 ML)，奈米團簇的密度與尺寸都隨著覆蓋率增加；在高覆蓋率(> 0.88 ML)，直徑不在變化，高度則有明顯的變化，伴隨著奈米團簇密度的稍微增加；加熱到450 K 之後 V 奈米團簇會變小。當溫度加熱到570 K和700 K 後，V 奈米團簇會形成更大的尺寸。V 金屬的奈米團簇有很好的排列行為，有著 bcc 的結構並且沿著平行Al2O3(100) 表面以 (110) 面方向成長，其 V 金屬奈米團簇的 [001] 方向平行於Al2O3(100) 的 [0-10] 方向 (V(110)[001]//Al2O3(100)[0-10])，晶格常數會隨著鍍量上升而有所上升，但會隨退火溫度上升而有所下降。

摘要(英)

Reactivity and selectivity of supported metal clusters in catalytic processes can be varied by controlling the cluster size. The size effect is thus centered in the studies of the nanocluster’s catalytic properties. To reveal origin of the size effect, a knowledge of the atomic structures of the nanoclusters is essential. The present work is devoted to controlling the size and resolving the structures at atomic level of vanadium (V) nanoclusters supported by ordered θ-Al_2 O_3 thin film grown on NiAl(100). We investigated the growth and thermal stability of V nanocluster grown on deposition of V vapor onto thin film θ-Al_2 O_3/NiAl(100) at 300 K, under ultrahigh vacuum conditions and with scanning tunneling microscope (STM) and reflection high energy electron diffraction (RHEED).The size of the V clusters increased with coverage: the mean diameter increased from 1.56 nm up to 2.07 nm, and the mean height from 0.46 nm to 0.66 nm at 300k. At low coverage (< 0.88 ML), the island density and average size of clusters increases with the coverage; at larger coverages (> 0.88 ML), the diameter does not change while the height increases significantly, accompanied with a slightly increase of cluster density. V nanoclusters become smaller after annealing to 450 K. With the temperature increasing to 570 K and 700 K, V atoms form larger clusters. The V clusters are structurally ordered, having a bcc phase, with their (110) plane parallel to the Al2O3(100) surface, and with [001] axes parallel to [0-10] direction of the Al2O3(100) (V(110)[001]//Al2O3(100)[0-10]). The lattice constant increases with the coverage and decreases with the annealing temperature.

關鍵字(中)

★ 釩
★ 氧化鋁
★ 高能電子繞射儀
★ 掃描穿隧式顯微鏡顯微鏡

關鍵字(英)

★ STM
★ RHEED
★ Vanadium
★ Al2O3

論文目次

Chapter 1 Introduction 01
Chapter 1 References 03
Chapter 2 Literature Survey 04
2.1 Al2O3 grown on NiAl(100) 04
2.1.1 NiAl crystal 04
2.1.2 θ-Al2O3 grown on NiAl(100) 07
2.2 Transition Metals supported on oxide surfaces 10
2.2.1 Au nanoclusters supported on Al2O3/NiAl(100) 10
2.2.2 Pt nanoclusters supported on Al2O3/NiAl(100) 17
2.2.3 Cu and V nanoclusters supported on Al2O3/Ni3Al(111) 20
2.2.4 V nanoclusters supported on Al2O3/NiAl(110) 24
Chapter 2 References 29
Chapter 3 Experimental Instrument and Procedures 34
3.1 Ultrahigh Vacuum (UHV) System 34
3.1.1 Introduction of vacuum 34
3.1.2 Introduction of UHV system 35
3.2 Reflection High Energy Electron Diffraction (RHEED) 38
3.3 Scanning tunneling microscope (STM) 42
3.3.1 Operation principles of STM 42
3.3.2 Operation of STM 45
3.3.3 RHK-UHV 300 STM 48
3.3.4 Preparing the STM tip 52
3.4 Experimental instruments 53
3.4.1 STM system 53
3.4.2 RHEED system 54
3.5 Experimental procedures 55
3.6 Estimation of coverage 58
Chapter 3 References 60
Chapter 4 Results and Discussions 62
4.1 The RHEED studies of V nanoclusters on Al2O3/NiAl(100) 62
4.1.1 The structure of V clusters on Al2O3/NiAl(100) 62
4.1.2 Coverage Effect of V nanoclusters on Al2O3/NiAl(100) 67
4.1.3 Annealing Effect of V nanoclusters on Al2O3/NiAl(100) 69
4.2 The STM studies of V nanoclusters on Al2O3/NiAl(100) 74
4.2.1 V nanoclusters on Al2O3/NiAl(100) 74
4.2.2 Annealed V clusters 81
Chapter 4 References 89
Chapter 5 Conclusions 90

參考文獻

M. Bäumer, H.-J. Freund, “Metal deposits on well-ordered oxide films”, Prog. Surf. Sci., Vol 61, pp. 127-198, August 1999.
R.M. Jaeger, K. Kuhlenbeck, H.-J. Freund, M. Wutting, W. Hoffmann, R. Franchy, H. Ibach, “Formation of a well-ordered aluminium oxide overlayer by oxidation of NiAl(110)”, Surf. Sci., Vol 259, pp. 235-252, December 1991.
P. Gassmann, R. Franchy, H. Ibach, “Preparation of a well ordered aluminum oxide layer on NiAl(001)”, J. Electron Spectrosc. Relat. Phenom., Vol 64-65, pp. 315-320, December 1993.
P. Gassmann, R. Franchy, H Ibach, “Investigations on phase transitions within thin Al2O3 layers on NiAl(001) – HREELS on aluminum oxide films”, Surf. Sci., Vol 319, pp. 95-105, November 1994.
R. Blum, D. Ahlbehrendt, H. Niehus, “Growth of Al2O3 stripes in NiA(001)”, Surf. Sci., Vol 396, pp. 176, January 1998.
J. Mendez, H. Niehus, “Growth of chromium on the structured surface of Al2O3/NiAl(100)”, Appl. Surf. Sci., Vol 142, pp. 152-158, April 1999.
N. Fremy, V. Maurice, P. Marcus, “ Initial Stages of Growth of Alumina on NiAl(001) at 1025 K”, J. Am. Ceram. Soc., Vol 86, pp. 669-675, April 2003.
N. Fremy, V. Maurice, P. Marcus, “X-ray photoelectron spectroscopy study of thin oxide layers formed on (001)-oriented β-NiAl single-crystal surfaces”, Surf. Interf. Anal., Vol 34, pp. 519-523, August 2002.
V. Maurice, N. Frémy, P. Marcus, “Hydroxylation-induced modifications of the Al2O3/NiAl(001) surface at low water vapour pressure”, Surf. Sci., Vol 581, pp. 88-104, March 2005.
W.C. Lin, C.C. Kuo, M.F. Luo, K.J. Song, M.T. Lin, “Self-aligned Co nanoparticle chains supported by single-crystalline Al2O3/NiAl(100) template” Appl. Phys. Lett., Vol 86, pp. 043105, January 2005.
M.F. Luo, C.I. Chiang, H.W. Shiu, S.D. Sartale, C.C. Kuo, “Patterning Co nanoclusters on thin-film Al2O3/NiAl(100)”, Nanotechnology, Vol 17, pp. 360-366, December 2005.
D.B. Miracle, “The physical and mechanical properties of NiAl”, Acta Metall. Mater., Vol 41, pp. 649-684, March 1993.
D.A. King, D.P. Woodruff (Eds.), “Chapter 4 Dynamics and diffusion of atoms at stepped surfaces”, Chem. Phys. Solid Surf., Vol. 8, pp. 102-148, 1997.
R. Franchy, “Growth of thin, crystalline oxide, nitride and oxynitride films on metal and metal alloy surfaces”, Surf. Sci. Rep., Vol. 38, pp. 195-294, 2000.
M.S. Zei, C.S. Lin, W.H. Wen, C.I. Chiang, M.F. Luo, “Growth of Al2O3 thin films on NiAl(100) by gas-phase oxidation and electro-oxidation”, Surf. Sci., Vol 600, pp 1942-1951, February 2006.
R.P. Blum, H. Niehus, “Initial growth of Al2O3 on NiAl(001)”, Appl. Phys. A, Vol 66, pp. S529-S533, 1998.
H.L. Davis, J. Noonan, “Rippled Relaxation in the (110) Surface of the Ordered Metallic Alloy NiAl”, Phys. Rev. Lett., Vol 54, pp. 566-569, February 1985.
M.F. Luo, H.W. Shiu, M.H. Ten, S.D. Sartale, C.I. Chiang, Y.C. in, Y.J. Hsu, “Growth and electronic properties of Au nanoclusters on thin-film Al2O3/NiAl(100) studied by scanning tunnelling microscopy and photoelectron spectroscopy with synchrotron radiation”, Surf. Sci., Vol 602, pp. 241-248, January 2008.
G.R. Hu, C.S. Chao, H.W. Shiu, C.T. Wang, W.R. Lin, Y.J. Hsu, M.F. Luo, “Low-temperature decomposition of methanol on Au nanoclusters supported on a thin film of Al2O3/NiAl(100)”, Phys. Chem. Chem. Phys., Vol 13, pp. 3281-3290, January 2011.
M. F. Luo, M. H. Ten, C. C. Wang, W. R. Lin, C. Y. Ho, B. W. Chang, C. T. Wang, Y. C. Lin, Y. J. Hsu, “Temperature-Dependent Oxidation of Pt Nanoclusters on a Thin Film of Al2O3 on NiAl(100)”, J. Phys. Chem. C, Vol 113, pp. 12419-12426, June 2009.
M.F. Luo, C.I. Chiang, H.W. Shiu, S.D. Sartale, T.Y. Wang, P.L. Chen, C.C. Kuo, “Growth of Co clusters on thin films Al2O3/NiAl(100)”, J. Chem. Phys., Vol 124, pp. 164709, April 2006.
S.D. Sartale, H.W. Shiu, M.H. Ten, J.Y. Huang, M.F. Luo, “Scanning tunneling microscopy study of growth of Pt nanoclusters on thin film Al2O3/NiAl(100)”, Surf. Sci., Vol 600, pp. 4978-4985, November 2006.
G. Medeiros-Ribeiro, A.M. Bratkovski, T.I. Kamins, D.A.A. Ohlberg, R.S. Williams, “Shape Transition of Germanium Nanocrystals on a Silicon (001) Surface from Pyramids to Domes”, Science, Vol 279, pp. 353-355, January 1998.
F.M. Ross, J. Tersoff, R.M. Tromp, “Coarsening of Self-Assembled Ge Quantum Dots on Si(001)”, Phys. Rev. Lett., Vol 80, pp. 984-987, February 1998.
M.F. Luo, W.H. Wen, C.S. Lin, C.I. Chiang, S.D. Sartale, M.S. Zei, “Structures of Co and Pt nanoclusters on a thin ﬁlm of Al2O3/NiAl(100) from reﬂection high-energy electron diﬀraction and scanning-tunnelling microscopy”, Surf. Sci., Vol 600, pp. 2139-2146, March 2007.
M. Klimenkov, S. Nepijko, H. Kuhlenbeck, M. Bäumer, R. Schlögl, H.-J. Freund, “Scanning tunneling microscopy study of growth of Pt nanoclusters on thin film Al2O3/NiAl(100)”, Surf. Sci., Vol 391, pp. 27-36, November 1997.
A. Wiltner, A. Rosenhahn, J. Schneider, C. Becker, P. Pervan, M. Milun, M. Kralj, K. Wandelta, “Growth of copper and vanadium on a thin Al2O3-film on Ni3Al(111)”, Thin Solid Films, Vol 400, pp. 71-75, 2001.
T. Worren, K. Højrup Hansen, E. Lægsgaard, F. Besenbacher, I. Stensgaard, “Copper clusters on Al2O3/NiAl(110) studied with STM”, Surf. Sci., Vol 477, pp. 8-16, April 2001.
M. Bäumer, J. Biener, R.J. Madix, “Growth, electronic properties and reactivity of vanadium deposited onto a thin alumina film”, Surf. Sci., Vol 432, pp. 189-198, March 1999.
C. Becker, K. von Bergmann, A. Rosenhahn, J. Schneider, K. Wandelt, “Preferential cluster nucleation on long-range superstructures on Al2O3/Ni3Al(111)”, Surf. Sci., Vol 486, pp. L443-L448, July 2001.
J. Libuda, F. Winkelmann, M. Bäumer, H.-J. Freund, Th. Bertrams, H. Neddermeyer, K. Müller, “Structure and defects of an ordered alumina film on NiAl(110)”, Surf. Sci., Vol 318, pp. 61-73, October 1994.
S. Stempel, M. Bäumer, H.-J. Freund, “STM studies of rhodium deposits on an ordered alumina film-resolution and tip effects”, Surf. Sci., Vol 402–404, pp. 424-427, May 1998.
J. Libuda, M. Frank, A. Sandell, S. Andersson, P.A. Brühwiler, M. Bäumer, N. Mårtensson, H.-J. Freund, “Interaction of rhodium with hydroxylated alumina model substrates”, Surf. Sci., Vol 384, pp. 106-119, July 1997.
Th. Bertrams, F. Winkelmann, Th. Uttich, H.-J. Freund, H. Neddermeyer, “Structural characterization of a model catalyst: Pt/Al2O3/NiAl(110)”, Surf. Sci., Vol 331–333, pp. 1515-1519, July 199.
M. Bäumer, J. Libuda, A. Sandell, H.-J. Freund, G. Graw, Th. Bertrams, H. Neddermeyer, Ber. Bunsenges, “The Growth and Properties of Pd and Pt on Al2O3/NiAl(110)”, Phys. Chem., Vol 99, pp. 1381-1386, November 1995.
M. Bäumer, M. Frank, J. Libuda, S. Stempel, H.-J. Freund, “Growth and morphology of Rh deposits on an alumina film under UHV conditions and under the influence of CO”, Surf. Sci., Vol 391, pp. 204-215, November 1997.
H.-J. Freund, B. Dillmann, D. Ehrlich, M. Haßel, R.M. Jaeger, H. Kuhlenbeck, C.A. Ventrice, F. Winkelmann, S. Wohlrab, C. Xu, T. Bertrams, A. Brodde, H. Neddermeyer, “Adsorption and reaction of molecules on surfaces of metal-metal oxide systems”, J. Mol. Catal., Vol 82, pp. 143-169, June 1993.
J. Libuda, M. Bäumer, H.-J. Freund, “Structural characterization of platinum deposits supported on ordered alumina films”, J. Vac. Sci. Technol. A, Vol 12, pp. 2259, December 1993.
A. Sandell, J. Libuda, M. Bäumer, H.-J. Freund, “Metal deposition in adsorbate atmosphere: growth and decomposition of a palladium carbonyl-like species”, Surf. Sci., Vol 346, pp. 108-126, February 1996.

指導教授

羅夢凡(Meng-Fan Luo)

審核日期

2018-3-28

推文