本研究乃利用一簡單的溼式化學方法(wet-chemcial route)，即首先利用水溶液化學浴沉積法(chemical bath deposition，CBD)，於FTO (fluorine-doped SnO2)基板上成長ZnO奈米線陣列(nanowire array)，之後再利用另一無鹼(base-free)化學浴沉積法，於奈米線陣列之表面異質成核與成長LBZA(layered basic zinc acetate)/ZnO奈米粒(nanoparticle)，以形成一同時具有良好電子傳輸特性與高表面積之奈米線-奈米粒複合薄膜。除此，藉由調變成長奈米粒之時間，也可輕易成長出三維(three-dimensional，3-D)的奈米線-奈米片(nanosheet)網狀結構、緻密的奈米線-奈米粒複合薄膜與表面含有花狀粒子的奈米線-奈米粒複合薄膜等不同奈米粒含量與表面型態之複合薄膜。根據X光繞射(X-ray Diffraction，XRD)與陰極發光(cathodoluminescence，CL)等分析，顯示複合薄膜內LBZA含量與ZnO缺陷濃度會隨成長奈米粒之時間增加而增加，且ZnO(002)繞射峰與紫外光發射頻帶之波峰位置也會隨奈米粒之成長時間不同而有所變化。此外，當奈米粒之成長時間超過16小時，複合薄膜內也會開始出現裂痕。吾人認為上述之現象乃由於氫氧基醋酸鋅錯化合物(zinc hydroxy-acetate complexes)之水解並不完全，導致所形成之ZnO奈米粒，c軸之晶格常數(lattice constant)會有所差異。根據高解析穿透式電子顯微鏡(high-resolution transmission electron microscope，HRTEM)之分析，證實ZnO奈米線與奈米粒間並沒有磊晶(epitaxial)之關係，因而吾人認為本研究能成功成長出奈米線-奈米粒複合薄膜之關鍵，在於利用無鹼化學浴沉積法，使LBZA會先異質成核於奈米線表面。
本研究也證實利用ZnO奈米線-LBZA/ZnO奈米粒複合薄膜作為光陽極，可大幅提升ZnO奈米線陣列染料敏化太陽能電池之效率。根據交流阻抗分析(Impedance analyses)，顯示ZnO奈米線-LBZA/ZnO奈米粒複合薄膜陽極之有效電子擴散係數(effective diffusion coefficient)介於ZnO奈米線陣列與TiO2奈米粒薄膜陽極之間。而ZnO奈米線-LBZA/ZnO奈米粒複合薄膜染料敏化太陽能電池之高效率，主要就是因為複合薄膜內同時含有奈米粒與單晶奈米線陣列，造成在大幅增加光利用效率的同時，卻未損失太多的電子傳輸效率。除了複合薄膜內奈米粒之含量，ZnO奈米線-LBZA/ZnO奈米粒複合薄膜染料敏化太陽能電池之效率還受複合薄膜厚度、複合薄膜內LBZA含量、ZnO缺陷濃度含量與裂痕含量等因素所影響。除此，本研究也發現複合薄膜內之LBZA含量，會受奈米粒成長時間與複合薄膜之退火處理條件所影響，且此LBZA含量在複合薄膜內之電子傳輸上乃扮演極為關鍵之角色。

ZnO nanowire (NW)-layered basic zinc acetate (LBZA)/ZnO nanoparticle (NP) composite films with different NP occupying extents have been synthesized using a simple wet-chemical route, i.e., aligned ZnO NW array first formed by an aqueous chemical bath deposition (CBD) and then heterogeneous nucleation and growth of LBZA/ZnO NPs on the surface of ZnO NWs by another base-free CBD. The features of the composites from three-dimensional (3-D) NW-nanosheet (NS) networks, dense NW-NP composite film to NW-NP composite film with flower-like particles are able to be obtained easily by varying the NP growth period. X-ray diffraction (XRD) and cathodoluminescence (CL) analyses indicate that the LBZA fraction and the ZnO defect concentration in the composite film are increased with the NP growth period in the base-free chemical bath solution. Shifts of the ZnO (002) diffraction peak and UV emission peak with the NP growth period are observed at the series of composite films as well. Moreover, cracks in the composites are also observed after NP growth for more than 16 h. We suggest those are attributed to the slight dissimilarity of the c-axis lattice constants of the ZnO NPs formed from a deficient hydrolysis of zinc hydroxy-acetate complexes. HRTEM analysis indicate that there is no epitaxial relationship between the ZnO NW and ZnO NPs, suggesting that heterogeneous nucleation of LBZA structure on the surface of the ZnO NWs is crucial for the formation of the NW-NP composite using the base-free route.
A significant improvement of the efficiency of the ZnO NW dye-sensitized solar cell (DSSC) has been also achieved using the ZnO NW-LBZA/ZnO NP composite film as photoanode. Impedance analyses of the electron transports in DSSCs reveal that the effective diffusion coefficient of an electron in the ZnO NW-LBZA/ZnO NP composite anode falls between those in the ZnO NW and TiO2 NP anodes. The superior performance of the ZnO NW-LBZA/ZnO NP composite DSSC to the ZnO NW cell is mainly ascribed to the enrichment of the light harvesting without significantly sacrificing the electron transport efficiency. In addition to the extent of NP occupying, the overall efficency of the ZnO NW-LBZA/ZnO NP composite DSSC is also influenced by the thickness of composite, the LBZA fraction, the defect concentration in ZnO and the cracks within the composite. The faction of LBZA in the composite film, which is affected by NP growth period and post-annealing conditions, is found to play a crucial role for electron transport through the composite as well.

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