本論文主要研究內容分為兩個部分，為改善奈米結構太陽能電池的轉換效率與氧化亞銅薄膜在奈米結構上的成長機制。首先，探討奈米結構導入太陽能電池可否如預期般的改善轉換效率。其主要的製程採用三極電鍍的技術，將氧化亞銅吸收層有效的填入氧化鋅奈米柱之間隙，來達到異質結構之p-n接面。在奈米柱的成長期間，作者觀察到硝酸鋅水溶液之濃度改變從10 mM到50 mM能有效的主導奈米柱的稀疏程度。再者，奈米柱的直徑與垂直長度也隨著時間的延長而增加，作者也利用上述的結果，調配出最佳化之條件應用於奈米結構太陽能電池。接下來，將氧化亞銅吸收層係以利用三極電鍍的方法沉積在奈米柱結構上，與文獻不同之處在於，使用物理沉積的技術，如：濺鍍、熱蒸鍍，無法有效的填補入密集奈米柱之間隙。作者使用的電鍍技術不僅大幅降低製程成本與設備之需求，最關鍵突破是將氧化亞銅薄膜完整填入稀疏或是密集的奈米柱中，故方能發揮奈米結構的優勢。另一方面，氧化亞銅薄膜其主要結晶相依循著奈米柱的稀疏程度而有大幅之改變。在稀疏的奈米柱上，氧化亞銅薄膜呈現為(111)的優先結晶相；相對的，在密集的奈米柱上則氧化亞銅薄膜轉換成(200)的優先結晶相。到目前為止，還未曾有相關研究與報導。因此，本實驗室設計了實驗對照組，嘗試去了解其原因。最終的結果，顯示為氧化亞銅晶粒之成長跟銅離子流有密切的相關性。當銅離子流供給方向與氧化亞銅晶粒成長方向平行，則晶粒將會延著銅離子供給方向做延伸，最終呈現(200)為主的結晶相，其特性為縱向的柱狀體；若銅離子流供給方向與氧化亞銅晶粒成長方向垂直，則晶粒也相對延著銅離子供給方向做延伸，最終呈現(111)為主的結晶相，其特性為橫向的丘陵狀。除了上述之發現，本實驗室也針對氧化亞銅的結晶性，在不同酸鹼值(pH)的環境或是改變其成長之電流，都將有深入的探討。
最後，作者也製作了多種奈米結構的太陽能電池元件，其接面結構如下：
Cell A. ITO/400 nm ZnO NRs/Cu2O
Cell B. ITO/300 nm ZnO/400 nm ZnO NRs/Cu2O
Cell C. ITO/300 nm ZnO/400 nm ZnO NRs/Cu2O (ZnO annealed at 400 ℃)
Cell D. ITO/80 nm ZnO/400 nm ZnO NRs/Cu2O
Cell E. ITO/300 nm ZnO/Cu2O (flat)
Cell F. ITO/300 nm ZnO/600 nm ZnO NRs/Cu2O

綜合以上之結果，我們利用奈米結構結合太陽能電池，確實改善了元件的特性；也提供電鍍製程，來解決文獻中所面臨的困境。最後，奈米結構太陽能電池之光電轉換效率在樣本D獲得0.56%，其開路電壓為0.514伏、短路電流密度為2.64毫安培及填充因子為41.5%。期望可對下世代的光電元件之開發提供助益。

This dissertation mainly investigates the proposed innovative process and improved Photovoltaic (PV) efficiency of nano-structured solar cells. The analysis is primary divided into two directions. First, we tried to ascribe how nanorod (NR) density influences on the Cu2O crystal orientation during electrochemical deposition (ECP). In order to fabricate different densities of non-doping ZnO NRs, the concentrations of Zn(NO3)2 from 10 mM to 50 mM could be used. During the ZnO NRs deposition, we observed that the Zn(NO3)2 concentration manipulated the density of NRs. In other words, the high-density of NRs will be obtained from a high Zn(NO3)2 concentration; low-concentration reveals sparse NRs. Subsequently, the Cu2O films were deposited on NRs substrate by electrochemical plating (ECP) process. The ECP process was chosen for the filling of the Cu2O film because ions in the solution can easily diffuse in between the gaps of the NRs. However, the transformation of Cu2O crystal orientation took place on different densities of NRs. The Cu2O film with (111)-preferred orientation can be obtained from a sparse NRs substrate, whereas, (200)-preferred orientation from a dense NRs substrate. Up to now, it is the first investigation about nano-rods density related to the crystal orientation of the ECP Cu2O films. To study why the Cu2O preferred growth is affected by the NRs, two electrodes, “perpendicular" and “parallel”, were used to deposit the Cu2O film with or without NRs on the ITO substrate. It has been found that the growth direction (or preferred orientation) of the Cu2O film can be manipulated by the Cu2+ ions flux. When the Cu2+ flux was perpendicular to the Cu2O nucleating surface, (200) will be the preferred orientation. On the other hand, when the Cu2+ flux parallel to the nucleating surface, Cu2O (111) is the dominated orientation. In this thesis, the influence of pH level and plating current on Cu2O preferred orientation were also investigated.
Second, three configurations of the nano-structured ZnO NRs/Cu2O solar cells were fabricated and studied. The cell configuration and sequence of the layers in the solar cell were as follows:
Cell A. ITO/400 nm ZnO NRs/Cu2O
Cell B. ITO/300 nm ZnO/400 nm ZnO NRs/Cu2O
Cell C. ITO/300 nm ZnO/400 nm ZnO NRs/Cu2O (ZnO annealed at 400 ℃)
Cell D. ITO/80 nm ZnO/400 nm ZnO NRs/Cu2O
Cell E. ITO/300 nm ZnO/Cu2O (flat)
Cell F. ITO/300 nm ZnO/600 nm ZnO NRs/Cu2O
The best photovoltaic efficiency of 0.56 % was obtained from cell D with Voc = 0.514V, Jsc= 2.64 mA/cm2 and 41.5 % fill factor.

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Chapter 7.
1 Otfried Madelung, Semiconductors : “Data Handbook”, Springer, 3rd edition, (2004).