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研究生： 吳志明
Jyh-Ming Wu
論文名稱： 二氧化鈦奈米線之性能、鑑定與成長研究
Performance, Characterization and Growth of TiO2 nanowires
指導教授： 施漢章
Han C. Shih
口試委員:
學位類別： 博士
Doctor
系所名稱： 工學院 - 材料科學工程學系
Materials Science and Engineering
論文出版年： 2005
畢業學年度： 94
語文別： 英文
論文頁數： 145
中文關鍵詞： 二氧化鈦 、奈米線 、奈米結構 、單晶
外文關鍵詞： TiO2, nanowires, nanostructure, single crystalline
相關次數： 點閱：3  下載：0 
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    • 本論文研究主要是以熱蒸鍍法製備單晶二氧化鈦奈米線與奈米柱，二氧化鈦奈米結構材料擁有獨特的電子、光學和機械特性之潛在應用，因此最近幾年有關二氧化鈦奈米結構如:奈米線、奈米柱與奈米粒子被廣泛的研究。本論文所製備之奈米結構材料，其內容涵蓋：二階段熱蒸鍍法合成二氧化鈦奈米線；氮氣混入法進行摻雜氮原子對二氧化鈦奈米線所造成之影響；二氧化鈦界面輔助層合成單晶奈米線以及奈米結構之各項光電性質鑑定。
    利用二階段式成長與二氧化鈦輔助層之熱蒸鍍法，二氧化鈦奈米線被成功地合成並且達成選區成長。對於二氧化鈦塊材與奈米線在陰極與光激光之特性光譜上，我們發現二氧化鈦之塊材呈現不發光現象。相反地，二氧化鈦單晶奈米線由於尺寸效應而具有藍位移之發光行為，此乃驗證單晶的特性造就其本質之發光行為。在摻雜氮原子進入二氧化鈦奈米線，吾人發現其光譜產生了紅位移之行為，紅位移現象也驗證了二氧化鈦奈米線之能帶縮小了。經由我們設計的合成方法，奈米線之結晶性質與比表面積均有明顯被改善，因此在光觸媒的應用分析上也顯著被提昇。在高倍率穿透式電子顯微鏡上發現二氧化鈦奈米線屬於單晶結構並延著[110]之熱力穩定方向成長。在利用摻雜金元素之二氧化鈦層，吾人測得二氧化鈦奈米線之電子場發射特性，其起始電場在5.7 V/μm時可得到電流密度10 μA/cm2。
    更重要地，對於氣相沉積法合成單晶二氧化鈦奈米線之成長機制在本論文中被徹底探討，對於本論文之研究成果將是值得進一步拓展於奈米元件之應用。

    Single crystalline TiO2 nanowires/nanorods were synthesized by radio frequency plasma enhanced physical vapor deposition (PVD). TiO2 nanostructured materials often have unusual electronic, optical and mechanical properties as well as a wide range of potential applications. This study encompasses: two-step thermal evaporation for growing TiO2 nanowires; incorporation of nitrogen (N) to the TiO2 during the growth and substrate effect of the TiO2 for the growth of the TiO2 nanowires; performance characterization in TiO2 nanostructures.
    The TiO2 layer and two-step thermal evaporation process were developed to grow the TiO2 nanwires. Accordingly, the selected-area growth of TiO2 nanowires was achieved. Both cathodoluminescence (CL) and photoluminescence (PL) indicated that TiO2 nanowires exhibit a blue shift of the emission peak owing to the size effect. Conversely, bulk TiO2 exhibited no luminescence. The nanowires exhibited luminescence, which was associated with their good crystallinity. The N-doped TiO2 nanowires was shown a red shift effect under CL examined. The red shift demonstrated that doping with nitrogen narrowed the band gap of TiO2 nanowires. The high photocatalytic activity of TiO2 nanowires can be obtained by increasing the specific surface area of nanowires and by improving their crystallinity. The high-resolution transmission electron microscopy (HRTEM) demonstrated that the nanowires are grown along the [110] axis, which is the most thermodynamically stable direction and to form the single crystalline TiO2. The Au-doped TiO2 layer enables to increase the electric conductivity. The electron field-emission properties of TiO2 nanowires are for the first time to be correlated by the Folwer-Nordheim (F-N) theory. A low turn-on field was thus found to be ~ 5.7 V/µm at a current density of 10 μA/cm2.
    More importantly, a mechanism of utilizing the vapor phase deposition for the synthesis of single crystalline TiO2 nanowires have been addressed throughout this work. It would be exciting to enlarge the current investigation into the studies of the nanodvice fabrication in the near future.

    Content 摘要 i Abstract ii Content iv Figure Captions vii Table Lists xii Chapter 1 Introduction 1 1.1 Nanotechnology 2 1.2 Size effect and low dimensional material 5 1.3 Nanostructure materials 7 1.4 Crystal structure of TiO2 (Rutile and Anatase) 11 1.5 Nitrogen dopants effect in TiO2 materials 16 Chapter 2 Literature Review 20 2.1 TiO2 nanostructure material 20 2.2 Motivation 20 2.3 An overview of theory and applications 22 2.3-1 Luminescent properties 22 2.3-2 Photoluminescence (PL) 25 2.3-3 Cathodoluminescence (CL) 26 2.3-4 TiO2 band gap structure 28 2.3-5 Photocatalytic properties in TiO2 material 30 2.3-6 Energy application in TiO2 material 32 2.3-7 Electron field emission properties 34 2. 4 Synthesized principle in TiO2 nanowires 35 2.4-1 Chemical process 35 2.4-2 Physics process 41 Chapter 3 Instrumentation and Characterization 44 3.1 Procedures for synthesizing TiO2 nanostructures 44 3.1-1 Preparing TiO2 nanowires by two-step thermal evaporation 44 3.1-2 In-situ observation of the TiO2 nanorods by two-step thermal evaporation 47 3.1-3 Ti buffer layer assisted growth of single-crystalline TiO2 nanowires 50 3.1-4 Doping TiO2 nanowires with nitrogen 52 3.1-5 Growth of TiO2 nanowires by two-step vaccum pressure 53 3.2 Instrumentation 54 3.2-1 DC sputtering for preparing Ti layer and Au catalyst 54 3.2-2 Radio frequency plasma-enhanced physical vapor deposition 54 3.3 Characterization 56 3.3-1 Thin film XRD diffractometer 56 3.3-2 Field emission scanning electron microscopy (FESEM) 56 3.3-3 Field emission transmission electron microscopy (FETEM) 57 3.3-4 X-ray photoelectron spectroscopy (XPS) 58 3.3-5 Raman spectroscopy 58 3.3-6 Luminescence analyzer 60 3.3-7 Ultraviolet visible (UV-vis) spectrophotometer 60 3.3-8 Field emission property analyses 61 Chapter 4 Results and Discussion 63 4.1 Synthesis of TiO2 nanowires by two-step thermal evaporation 63 4.2 In-situ observation of the TiO2 nanorods by two-step thermal evaporation 67 4.3 CL properties in single-crystalline TiO2 nanowires/nanorods 72 4.4 TiO2 buffer layer assisting growth of TiO2 nanowires 75 4.5 Photoluminescence properties in TiO2 nanowires 81 4.6 The CL properties in nitrogen doped effect of TiO2 nanowires 83 4.7 Comparing the photocatalytic activities of single crystalline rutile TiO2 nanowires and mesoporous anatase paste 86 4.8 The electron field emission property in TiO2 nanowires 94 4.9 Formation mechanism 101 4.9-1 Two-step growth mechanism 102 4.9-2 Two-step vacuum pressure growth mechanism 103 Chapter 5 Summary and Future work 107 5.1 Summary 107 5.2 Future Work 109 Reference 111 Publication List 130 Vita 133 Figure Captions Fig. 1.1 Schematic the organization of nanostructure [11] 3 Fig. 1.2 A self-cleaned function of the lotus effect [12] 4 Fig. 1.3 Low dimension material definition [13] 6 Fig. 1.4 SEM image of TiO2 nanotube arrays on silicon substrate, (a) top view and (b) side view of nanotubes with outer diameters of 40nm, heights of ~ 1.5 μm, and average center-to-center tube spacing of ~ 60 nm, (c) top, and (d) oblique views of a hexagonally ordered array of nanotubes with outer diameters of 80 nm, heights of ~ 300 nm, and average center-to-center tube specing of ~100 nm. The inset in (d) shows a side view of the tubes on the substrate [14]. 8 Fig. 1.5 (a) A typical HRTEM image of a single TiO2 nanotubes, and (b) A schematic model for the formation of TiO2 nanotubes [22]. 9 Fig. 1.6 Three polymorphs of TiO2 [34] 12 Fig. 1.7 Octahedra-packing diagram for rutile TiO2 [35] 15 Fig. 1.8 Crystal structure of rutile and anatase. 15 Fig. 1.9 Schematic representation of the 110 surface of titanium dioxide. Titanium atoms are indicated by dark spheres, oxygen atoms by the light spheres. The unit cell measures 6.5 Ǻ along and 2.96 Ǻ along [46]. 15 Fig. 1.10 Mechanistic principles for the degradation of pollutants, Radiative and nonradiative as well as photocorrosion processes are omitted for the soak clarity [50]. 18 Fig. 2.1 Radiative band-to-band recombination in (a) direct gap and (b) indirect gap semiconductor [73] 25 Fig. 2.2 Front–surface photoluminescence analyzer with lenses [74] 26 Fig. 2.3 Illustration CL observed in an electron microscope [75] 28 Fig. 2.4 illusations the energy band (a) insulator, (b) typical semiconductor, and (c) conductor [6]. 29 Fig. 2.5 Band edge position of semiconductor materials [77] 30 Fig. 2.6 Photocatalytic reactions is an efficient photochemical conversion process [79] 32 Fig. 2.7 Showing the operational principle of such a device [58] 33 Fig. 2.8 (a) Preparation process of TiO2 nanotubes. SamplesA and B: samples collected after treatment with 10 M NaOH (aq.) when the conductivities of the supernatant reached 10 mS/cm and 70 µS/cm, respectively. Sample C: collected after addition of HCl, when the conductivity reached 800 µS/cm. Sample D: collected when the conductivity reached ~10 µS/cm. DW = distilled water [87]. 37 Fig. 2.8 (b) TiO2 were formed by rolling up the anatase single-wall of sheet [88]. 38 Fig. 2.9 (a) SEM image of the TiO2 nanowires grown in a 50 nm diameter membrane, and (b) Raman spectra of the untreated and annealed bulk nanowires sample samples. All of the AAO template were removed [89]. 39 Fig. 2.10 TEM images of nanowires and SEM images of AAO template that we used in our experiment. (a) TEM images of 20 nm TiO2 nanowires, (b) TEM images of 10 nm TiO2 nanowires, (c) TEM image of a single TiO2 nanowire with a diameter of about 40 nm and the corresponding selected area diffraction pattern of this nanowire (inset), (d) SEM images of 50 nm AAO template, (e) SEM images of 22 nm AAO template, and (f) SEM images of 12 nm AAO template. The scare bars in D, E, and F are 500 nm [89]. 40 Fig. 2.11 Schematic drawing showing the preparation of an array of TiO2 pillars: (a) imprinting a TiO2 wafer using a SiC mold, (b) array of concave dimples formed on TiO2, and (c) photoetching of the textured TiO2 and the array of TiO2 pillars obtained [90]. 42 Fig. 3.1 Two-step thermal evaporation process flow chart. 46 Fig. 3.2 Schematic diagrams showing: (a) as the first-step, the sample covered with 0.5 g titanium powder at HT zone in the graphite boat, and (b) as the second-step, the new titanium powder 0.5 g and the sample separated to locate at HT zone and LT zone on the graphite boat, respectively. 47 Fig. 3.3 Two-step thermal evaporation process flow chart for growing the nanobricks and nanorods 49 Fig. 3.4 Schematic diagrams: (a) in the first step, the sample is covered with 1 g titanium powder in the HT zone in the graphite boat, and (b) In the second step, 1 g of the new titanium powder and the sample were separated from each other in the HT zone and the low-temperature (LT) zone of the graphite boat, respectively. 49 Fig. 3.5 Schematic diagram for RF heater synthesis system, Ti powder and as-prepared substrate separated from each other to locate the graphite boat in the HT zone and the LT zone. 51 Fig. 3.6 Ti buffer layer assisted growing nanowires process 52 Fig. 3.7 Process flow chart of the two-step vacuum pressure 54 Fig. 3.8 (a) Furnace of RF heater with the vacuum system, (b) sketch for PVD furnace system. 55 Fig. 3.9 FESEM JOEL 7000 57 Fig. 3.10 FETEM JEM-2000FX 58 Fig. 3.11 (a) The Raman spectroscopy (Jobin Yvon T64000), (b) block diagrams of the generic components making up a Raman spectrometer [94]. 59 Fig. 3.12 (a) UV-visible spectrophotometer (HITCHI U-2800), (b) showing the optical system of U-2800 mode. 61 Fig. 3.13 The electron field emission measurement system [95]. 62 Fig. 4.1 FESEM image showing that the sample of TiO2 nanowires were grown on alumina substrate, having diameters in the range of 60-90 nm and lengths of hundreds of nm to 2 µm. 65 Fig. 4.2 Thin film X-ray diffraction pattern revealing that the TiO2 nanowires are composed of rutile phase. The alumina phase is attributed from the substrate. 65 Fig. 4.3 Raman spectrum showing the composition of TiO2 nanowires belonging to the rutile structure. The characteristic modes are located at the position of 143, 240, 447, and 610 cm-1. 66 Fig. 4.4 HRTEM images showing (a) an individual TiO2 nanowire, (b) lattice fringe of the nanowire growing on the [110] direction, (c) the SAD of (110) plane showing the single crystallinity of the nanowire, and (d) the corresponding rutile structures, with a fringes spacing of 0.32 nm. 66 Fig. 4.5 FESEM images of TiO2 nanobrick/nanorods deposited on alumina substrates at various growing times in the two-step process. (a) High surface energy of TiO2 nanoclusters in the first step. (b), (c) and (d) second step of the process, after growing times of 10 minutes, 20 minutes and 40 minutes, respectively. 70 Fig. 4.6 (a) TEM image of an individual TiO2 nanorod with twinning structure (b) Electron diffraction pattern of the nanorod, which is a perfect single crystal with twin parts. The solid and dotted lines have a mirror symmetric relationship with each other. (c) HRTEM reveals a lattice spacing of around 0.32nm. 70 Fig. 4.7 Raman spectra of (a) the TiO2 nanobricks after growing time of 20 minutes, and (b) TiO2 nanorods after growing time of 40 minutes 71 Fig. 4.8 The CL spectra at room temperature resulting from the TiO2 nanowires. The peaks are located at the wavelength 418, 465, 536 and 834 nm. 74 Fig. 4.9 The low-magnification FESEM images indicated that the TiO2 nanowires grew with high aspect ratios over the entire substrate, with lengths of up to 3 µm, (a) with diameters in the range 60-90 nm, and (b) TiO2 nanowires grown on the substrate anisotropically. 76 Fig. 4.10 Thin film X-ray diffraction pattern, revealing that the TiO2 nanowires consisted of the rutile phase. 76 Fig. 4.11 Low-magnification TEM image of the TiO2 rutile showing Au nanoparticles; the black circle area corresponding to the insets (a) and (b). (a) HRTEM image showing the (110) plane, corresponding to the parallel fringe spacing of 0.32 nm, and (b) corresponding selected-area electron diffraction pattern, indicating that the single crystalline nanowire grew in the [110] direction. 80 Fig. 4.12 FESEM image, indicating that the nanowires were not grown successfully on the left side, which is coated with gold as a catalyst and does not have the deposited Ti layer. 80 Fig. 4.13 PL spectra showing an emission peak at approximately 380 nm. 82 Fig. 4.14 The CL spectra, revealing that un-doped TiO2 nanowires (NWs) have an emission peak at ~ 402 nm; N-doped TiO2 nanowires have a peak at ~ 439 nm, and bulk TiO2 has a peak at ~ 534 nm. The 439 nm peak of the N-doped nanowires is a red shift if compared with 402 nm peak of the un-doped nanowires, both nanowire emission peaks indicating a blue shift in contrast to the broad band of bulk TiO2 (534 nm). 85 Fig. 4.15 XPS spectra from N-doped and un-doped spectra; the N 1s peak is associated with N-doping effect. 86 Fig. 4.16 (a) FESEM image showing that the TiO2 nanowire are grown all over the substrate, and (b) the anatase TiO2 paste showing a mesporous morphology. 89 Fig. 4.17 XRD spectrum (a) TiO2 rutile phase nanowires, and (b) TiO2 paste anatase phase. 89 Fig. 4.18 TEM image showing an individual TiO2 nanowires with branch-like, (a) SAD pattern, and (b) lattice image 90 Fig. 4.19 TEM image and SAD pattern showing the polycrystalline nature of the anatase nanoparticles. 90 Fig 4.20 (a) Transmission spectra of the methylene blue solution, and (b) decomposition rate of the methylene blue solution after the photodegradation by rutile nanowires and anatase paste. 93 Fig. 4.21 (a) Oblique view of FESEM image, indicating the nanowires were grown all over the substrate, inset a side image revealing that the TiO2 nanowires were grown on the Au-doped TiO2/Si substrate, and (b) Thin film X-ray diffraction pattern, revealing that the TiO2 nanowires consisted of the rutile phase. 95 Fig. 4.22 (a) TEM image, the Au particles indicating that a VLS mechanism governs the growth of TiO2 nanowires, (b) HRTEM lattice image, and (c) corresponding SAED pattern. 96 Fig. 4.23 Au-doped TiO2 layer of cross-sectional image was obtained by TEM, (a) the high-angle annular dark field STEM image, clearly showing a densely scattered high-Z contrast Au dots; the corresponding EDS mapping of (b) Au, (c) Ti, and(d) Si (substrate). 97 Fig. 4.24 (a) J-E field emission plot from TiO2 nanowires; with the corresponding F-N plot inset, and (b) the phosphor screen showing the spatial distribution of the emission sites for TiO2 nanowires. 101 Fig. 4.25 Au clusters (white dots) are highly scattered on the surface of the TiO2 layer. 105 Fig. 4.26 Au clusters (black spots) are embedded into the polycrystalline TiO2 layer 105 Fig. 4.27 Embedding of Au clusters (a) vacuum pressure at 1 Torr, (b) vacuum pressure at 600 Torr, and (c) TiO2 layer underwent re-crystalline, and Au dots were widely scattered throughout the TiO2 layer. 106 Table Lists Table 1.1 TiO2 structure data [34] 16 Table 4.1 BET specific surface area resulting from the rutile nanowire and anatase paste of the TiO2. 91

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