臺灣博碩士論文加值系統

在本論文研究中，氧化鋅/硫化銅奈米結構分別採用原子層沉積法（ALD）及化學浴沉積法（CBD）製備而成。氧化鋅奈米柱ALD沈積使用二乙基鋅（DEZn）和氧化亞氮（N2O）前驅氣體將氧化鋅(ZnO)奈米柱沈積在c面藍寶石基板（c-plane sapphire）。硫化銅殼層結構則使用硫酸銅與硫代硫酸鈉溶液以CBD生長於氧化鋅奈米柱側壁。氧化鋅/硫化銅奈米結構之樣品分別採用高解像能穿透式電子顯微術（HRTEM）,掃描式電子顯微術（SEM）,X-射線繞射分析（XRD）分析其物理特性以及表面形貌。研究結果發現氧化鋅/硫化銅 核心/殼層結構可透過ALD-ZnO及CBD-CuS的沈積方式合成。

In this thesis, ZnO/CuS nanostructures were achieved by atomic-layer deposited (ALD) ZnO nanorods and chemical bath deposited(CBD) CuS shells. In this case, ZnO nanorods were deposited on a c-plane sapphire substrates by ALD, using diethylzinc (DEZn) and nitrous oxide (N2O) as precursors. CuS shells were then deposited on the side walls of ZnO nanorods by CBD using mixed copper sulfate and sodium thiosulfate solution. The physical properties and surface morphologies of ZnO /CuS nanostructures were investigated by high resolution transmission electron microscopy(HRTEM), scanning electron microscopy (SEM) and x-ray diffractometry (XRD). It was found that the ZnO/CuS core/shell structures had been successfully synthesis by the method of CBD

Table of contents
致謝辭...................................................i
中文摘要 ...............................................ii
Abstract ...............................................iii
Table of contents ......................................iv
List of tables .........................................v
List of figures.........................................vi
Chapter 1 Introduction .................................1
Chapter 2 backgrounds...................................3
§2-1 Introduction of nanomaterials......................3
§2-2Physical properties of ZnO..........................9
§2-3 Literature review of core/shell semiconductor structures..............................................12
§2-4 Motivation of this thesis...................................................14
Chapter 3 Experimental procedures and analytical tools..15
§3-1 Substrate cleaning.................................15
§3-2 Growth of ZnO nanostructures by ALD................16
§3-3 Deposition of CuS by CBD...........................20
3-3-1Chemicals for CBD................................20
3-3-2 Preparation of CBD solution for CuS growth......20
3-3-3 Experimental process of CuS film deposition..............................................20
3-3-4 Process of baking..................................................21
3-3-5 The annealing process of CBD-deposited CuS......22
§3-4Chatacterization tools..............................22
3-4-1 X-ray diffractometry.............................22
3-4-2Scanning electron microscopy (SEM)................23
3-4-3Transmission electron microscopy (TEM)............23
3-4-4TEM sample preparation............................23
Chapter 4 Results and discussion .......................27
§4-1Characterization of ZnO/CuS nanostructures .........27
§4-2 High-resolution TEM study of ZnO/CuS nanostructures..........................................30
Chapter 5 Conclusion and future works...................37
References..............................................38
List of tables
Table2-1The physical properties of ZnO.....................................................11
Table4-1A list of the chemical contents in the selected area of the ZnO/CuS nanostructure.......................34
List of figures
Figure 2-1 Zero-dimensional gold nanoparticles..........6
Figure 2-2 One-dimensional nanostructure: (a) ZnO nanobelt(b)ZnO nanorods.........................................7
Figure 2-3 Two-dimensional nanostructured tin oxide nanometer bowl .........................................7
Figure 2-4 (a) ZnO nanorods,(b)a schematic diagram of a ZnO nanorod film field effect transistor,and (c) a schematic diagram of a dye-sensitized solar cell using a ZnO nanorod array as a substrate....................................8
Fig2-5 ZnO structure....................................10
Fig2-6 A type-I & type-II energy band diagram...........13
Fig2-7 An example of a type II..........................13
Fig. 3-1 A schematic of the home-made ALD system in this study...................................................17
Fig. 3-2 A schematic diagram of graphite base and precursor injections..............................................18
Fig. 3-3 Temperature vs. time plot of the deposition process of ZnO/ZnS core-shell structure using double buffer-layer structure.........................................18
Fig. 3-4 A cross-sectional schematic of ZnO grown on (0001)-sapphire substrate.....................................19
Fig. 3-5 A photo of a D8 Discover SSS x-ray diffractometer..........................................24
Fig. 3-6 Schematic of the symmetric GID geometry........25
Fig.3-7 A photo of a JEOL JSM-6700F field –emission scanning electron ......................................25
Fig.3-8 A photo of a JEOL JEM-2010F field-emission high-resolution transmission electron microscope.............26
Fig.3-9 A schematic of TEM sample preparation process...26
Fig4-1 A SEM image of ZnO at low magnification nanostructures..........................................27
Fig4-2 A SEM image of ZnO nanostructures................28
Fig4-3 A SEM image of ZnO/CuS nanostructures............28
Fig4-4 A XRD plot of ZnO/CuS as-deposited by CBD........29
Fig 4-5 A XRD plot of ZnO/CuS annealed at 400oC for 30 min.....................................................29
Fig4-6 A HRTEM image of ZnO/CuS core-shell nanostructure...........................................31
Fig4-7 A TEM image of ZnO/CuS core-shell nanostructure with the thickness of CuS being~70 nm........................31
Fig.4-8 The (a) bright-field TEM image and (b)its selected area diffraction (SAD) pattern of the ZnO/CuS nanostructure...........................................32
Fig4.9 A selected area of the ZnO/CuS nanostructure for EDS analysis................................................33
Fig4-10 Energy-dispersive spectroscopy(EDS) data of the selected ZnO/CuS nanostructure..........................33
Fig4-11 A HRTEM image of the ZnO/CuS nanostructure .....34
Fig4-12 An enlargement of the HRTEM image showing the interplanar spacing of (002)ZnO being 0.26 nm...........35
Fig4-13 An enlargement of the HRTEM image showing the interplanar spacing of (103)CuS being 0.28nm............36

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