本論文旨在研究一維氧化鎢(WOx)、金屬鎳(Ni)、氧化鋅(ZnO)奈米線之成長製備暨其電子、光電元件之應用及相關特性之研究。在研究中，我們提出以簡易的爐管熱處理方式自組式成長WOx奈米線，這種方法只需經由沉積純鎢(W)薄膜於矽基板上，在適當的實驗條件下，即可以大面積製作高密度(約250 mm-2)、長度與直徑約0.2 贡m/20 nm 的WOx奈米線。然利用此種熱處理方式成長之WOx奈米線，常因在製程中(薄膜沉積或是熱退火)，表面吸附大量氧氣，導致WOx奈米線之電子場發射特性未臻理想。為改善WOx奈米線之場發射特性，本研究乃提出利用氫電漿處理以改善WOx 奈米線電子場發射特性，藉由適當之氫電漿處理，降低WOx奈米線表面之氧含量，並同時修飾與純化奈米線表面結構。此外，透過SEM、TEM、SAED、及XPS等工具，對WOx奈米線進行分析，探討WOx奈米線中各項物性、化性等對場發射特性的影響，並於本研究中提出相關物理機制之說明。
為了改善奈米線之電子場發射特性，我們另採用一低功函數之金屬鎳(Ni)奈米線當作是電子場發射之陰極材料。本研究中，利用電鍍製程搭配陽極氧化鋁(AAOTs)模板所成長的Ni奈米線，所得之奈米線成長密度介於1.5-2.1 109 cm-2，其長度與管徑則分別介於2.7-22 贡m與100-200 nm之間。除了具有高筆直性外，於長寬比、均勻度甚或密度等方面均較容易獲得控制。由於AAOTs具有筆直的奈米孔洞，當Ni奈米線於孔洞內成長後，只要在AAOTs模板上蓋上電極金屬作為正極，即可以近似AAOTs孔洞的厚度(~60 贡m)作為此電子場發射之間距。量測結果顯示在AAOT基板上成長之Ni奈米線，除了具有絕佳的方向性外，且具備優異之二極場發射特性，此一特性足以媲美傳統奈米碳管之場發射特性，也將會是未來相關領域場發射元件的最佳方案。另外，於研究中也將AAOTs模板移除，進一步於實驗中討論AAOTs模板對於場發射特性之影響，經由場發射電壓電流特性之量測可得知，移除AAOTs模板後的Ni奈米線試將會大幅的改善Ni奈米線之場發射特性，其所測得場發射特性之enhancement factor (刍)將比未移除AAOTs模板試片大於57.6%，相關的機制說明將於本論文中做一詳細之討論。
本研究亦提出一種整合AAOTs製作與電鍍沉積及氧化技術之異質接面奈米線結構之製作方法，藉由一維結構之奈米線異質接面之量子效應，將可有效提升元件之光電響應能力。本研究主要是將金屬鎳(Ni)及金屬鋅(Zn)依序電鍍沉積於AAOTs之奈米孔洞內，形成長度可調之Ni/Zn異質接面結構奈米線(Ni/Zn-NWs)；再經適當之氧化製程，將奈米線整體氧化成具有p-type形態之氧化鎳(NiO)半導體與具有n-type形態的氧化鋅(ZnO)半導體。本研究所提出p-NiO/n-ZnO異質接面奈米線結構之製備方式，不需傳統昂貴之磊晶或是長晶製程，及具有不需觸媒、製程簡易與長度可控之優點。於實驗中亦透過Ni/Zn異質金屬接面奈米線及NiO/ZnO異質接面奈米線結構之光電特性量測結果，利用照光(UV光((254nm, 366 nm)與不照光(dark)的量測轉變，可以很明顯的發現本實驗所製作的Ni/Zn異質金屬接面奈米線及NiO/ZnO異質接面奈米線結構，對於UV入射光線具有很明顯的光電流(阻)變化。
為持續提升奈米線之光電元件應用與降低製程之複雜度及成本，本研究亦提出一種整合水熱法成長ZnO奈米線與NiO金屬鍍著技術，以ZnO奈米線為基材之NiO/ZnO奈米線異質接面結構之製作方法。以水熱法成長之ZnO奈米線具有低製程溫度(<90oC)，不致降損元件元件之光電性能；且成長方式無需觸媒，於大面積基板上具垂直自我成長之特性，於大面積光電元件製作上具有極大優勢。透過水熱法方式成長所得之ZnO奈米線除了可以獲得垂直排列之ZnO奈米線外，於ZnO奈米線之長寬比、均勻度甚或密度等方面均較容易獲得控制。本研究中也將研究ZnO奈米線之成長製備方式以及其相關物性及化性特性的瞭解。成長垂直基板之ZnO奈米線後，搭配NiO金屬鍍著技術，形成NiO/ZnO奈米線異質接面結構。本實驗中，藉由NiO/ZnO奈米線異質接面結構照UV光與模擬太陽光(AM1.5)及不照光(dark)的量測結果，可以明顯的發現本實驗所製作的NiO/ZnO奈米線異質接面結構，對於UV入射光線具有很明顯的光電流變化。同時，在模擬太陽光(AM1.5)的作用下，可以觀察到元件明顯的光電壓特性。而實驗中各項分析結果顯示，奈米異質接面結構中，適當的材料選擇及搭配為成長製備未來奈米光電元件之關鍵因素。
於光電元件的應用上，一般as-grown ZnO奈米材料為一直接能隙n-型半導體材料，其能隙為3.37 eV，激子結合能為60 meV，較其他半導體材料擁有較大之光電轉換效率；此外，一維結構的ZnO奈米線具有量子侷限效應與高表面積/體積比率，可進一步提高光電元件性能及光電轉換效率，為一極具潛力之光電元件材料。基此，應用ZnO奈米線於薄膜太陽電池之開發製作已快速激起原先以矽半導體為主流之太陽能應用領域之注意，而相關研究開發活動亦已如火如荼展開中。針對ZnO奈米線於太陽電池之應用，本研究提出一利用水熱法成長ZnO奈米線於GaN基板上，形成p-GaN/n-ZnO奈米線太陽能電池元件結構及此太陽能電池元件量測之光電特性及轉換效率研究。因為ZnO與GaN兩種材料具有相近的能隙寬度、晶格常數、及良好的晶格匹配等特性，p-GaN/n-ZnO奈米線太陽能電池元件所得之開路電壓、短路電流與效率皆已達到近期奈米線材料特性研究之水準，顯示此p-GaN/n-ZnO奈米線太陽能電池元件具有價值性與創新性，為薄膜太陽電池製作並提升其光電特性上提供另一新穎材料與技術之選擇。

In this thesis, the growth and physical/chemical properties of one-dimensional tungsten oxide nanowires (TONWs), nickel nanowires (NiNWs), zinc oxide nanowires (ZnO-NWs) were investigated. This study also proposes the use of a these NWs structures for potential in applications of nano electronic and optoelectronic devices. In the first study, for the growth of TONWs, pure tungsten films with a thickness of 60 nm on n-type Si wafers were subjected to thermal annealing in a quartz tube furnace at 700oC in nitrogen ambient for 30 min. After thermal annealing, straight TONWs with a density of around 250 贡m-2 and length/diameter of around 0.2 贡m/20 nm were obtained. However, oxygen adsorption might arise from the oxygen contamination of source material during wire growth, the residual oxygen in sputtered films or intentionally doped oxygen gas during sputtering deposition, and oxygen/humidity adsorption of the grown TONWs. In this study, H-plasma treatment is used to reduce the amount of oxygen adsorption and to tailor the density and morphologies of TONWs. Improved field emission (FE) characteristics are demonstrated and the related reduction in the effective emission barrier height is analyzed and discussed.
In general, FE current is a complex function of the work function, tip shape, diameter, length, and density of the emitter array. All of these factors affect the local field around the tip of nanowires and hence the FE current. In the previous study, the as-grown TONWs with a typical work function of 6.2 eV and their FE characteristics have been studied. Nanowires with a lower work function are expected to give better FE characteristics. So NiNWs with a lower work function of 5.15 eV are used as new electron field emitters. Well-ordered and vertically-aligned NiNWs with a controllable length in the range of 2.7~22 mm and high density of 1.5-2.1 109 cm-2 were grown inside the nanopores of anodic alumina oxide templates (AAOTs) using a simple electrochemical deposition (ECD) method. To measure electron FE characteristics of the prepared NiNWs, 60-mm-thick AAOTs were served as an insulating spacer. The relatively better FE characteristics with a turn-on field and the enhancement factor of 8.5-贡m-long NiNWs prepared within 100 pore diameter AAOTs were about 3.46 V/mm and 17621, respectively. It is expected that NiNWs prepared inside the nanopores of AAOTs with controllable diameters and lengths could offer an additional choice of material for electron field emitter applications. In addition, in order to obtain the pristine vertically-aligned NiNWs for FE characteristics measurements, the AAOTs were removed and the electron FE characteristics of the prepared NiNWs before and after removing the AAOTs were measured and discussed. After removing the AAOT, NiNWs showed better electron FE characteristics than the others within the AAOT. The effect of the aluminum oxide pillars on the FE characteristics of NiNWs has been examined, and their removal might make possible the immunity of FE electrons collision and accumulation on the vertical surface of the pillars, leading to a significant improvement in the FE performance.
Recently, nano heterostructured materials have attracted lots of attention because of the quantum confinement effects of nano heterojunctions (NHJs) and for their potential applications on quantum optoelectronic devices. In this study, well-ordered and vertically-aligned NiO/ZnO NHJs were grown inside the nanopores of AAOTs using ECD and thermal oxidization. This synthesis method presents a simple and novel method for the self-synthesis of NHJs NWs without using catalysts, easily growing and the length of NWs can be controlled accurately. The electrical characteristics of NiO/ZnO NHJs show a rectifying behavior of a p-n junction, while the Ni/Zn NHJs show an ohmic behavior. The optoelectronic characteristics of NiO/ZnO NHJs show a well rectifying behavior and strong photo response to the ultraviolet (UV) lights (254 and 366 nm). Possible carrier transport of the NiO/ZnO NHJs under UV light irradiation is analyzed and discussed. Because of less dimension of the NiO/ZnO NHJs show profound quantum confinement effect, these devices are expected to exhibit much better optoelectronic performance than conventional planar devices.
In order to improve the optoelectronic properties of the NHJs and to overcome the processing expensive and time consuming, a novel technology using hydrothermal growth (HTG) associated with deposition techniques for the fabrication of nano hetero structure based on ZnO nanowires (ZnO-NWs) is reported in this study. The HTG method is the most commonly used for commercial applications because of their low cost of equipment, large-area and uniform fabrication, and low processing temperature. NiO/ZnO-NWs NHJs were formed via e-beam deposition of p-type NiO onto the vertical-aligned ZnO-NWs grown by HTG method. Furthermore, the use of a ZnO-NW-based heterojunction structure for applications of nano optoelectronic sensors and photovoltaic devices was proposed. The optoelectronic properties of the NiO/ZnO-NWs NHJs with different NiO thicknesses under UV light (366 nm, 6 mW/cm2) illumination, with good UV sensitivity were analyzed and discussed. Under simulated AM 1.5G solar light illumination, the fabrication of NiO/Zn-NWs NHJs solar cell and its photovoltaic characteristics were also presented.
Finally, ZnO with a wide direct bandgap (3.37 eV) and a large excitation biding energy (60 meV) is a promising n-type semiconductor material for applications of light emitting diodes, sensors, and solar cells. In addition, ZnO-NWs are widely used to yield better efficiency for sensor and solar energy than thin films because of their nanosized structures, high integration, high surface active area, attractive optoelectronic properties, and the profound quantum confinement effect. For the application of photovoltaic and solar cell devices, the growth of ZnO-NWs with controllable diameter/length/density and fabrication of n-ZnO-NWs-based NHJs with p-type GaN are studied. A number of ZnO-NWs/p-GaN NHJs have been studied as a strong candidate for optoelectronic device applications, since these materials (ZnO and GaN) have similar fundamental bandgap energy, the relatively close physical properties, and a low lattice constant mismatch. Under AM 1.5G solar light illumination, the fabrication of n-ZnO-NW/p-GaN solar cells and their photovoltaic characteristics with different lengths of ZnO-NW were analyzed. Effects of the length of ZnO-NWs on the photovoltaic performance of the ZnO-NWs/p-GaN NHJs were also investigated and discussed.

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