本論文旨在減緩載子複合以及利用階層式奈米結構增進元件光吸收以提高黃銅礦光伏元件之效能。內文首先簡介太陽能產業現況發展及銅銦鎵硒光伏元件優勢，並於現有元件製程的基底上提出四大方向進行元件效能增益技術的研發。第一部分使用斜角蒸鍍系統沉積自組裝氧化鋁奈米結構於超薄銅銦鎵硒吸收層與鉬背電極的界面做為減緩背向複合的鈍化層，由於氧化鋁自身攜帶的負電荷能夠將銅銦鎵硒吸收層內產生之少數載子反彈回p-n接面，達成減緩背向複合的效果，而氧化鋁奈米結構的設計也能夠減緩前人研究中使用氧化鋁薄膜造成的電阻及缺鈉效應。此外，研究結果更發現此氧化鋁奈米結構後會造成後續沉積之銅銦鎵硒吸收層產生相變化，減緩後硒化製程製備之銅銦鎵硒薄膜常見的分相問題。整體而言，引入氧化鋁奈米結構後的超薄銅銦鎵硒元件效率能夠從2.83 %大幅提升至5.33 %。第二部分則引入電漿子奈米粒子至吸收層中，以期透過電漿子效應以及散射效應增強銅銦鎵硒層的吸收。實驗中使用金-二氧化矽核殼結構奈米粒子，避免在高溫硒化過程中金與銅、銦、鎵等前趨物產生合金反應。實驗結果顯示在使用最薄的二氧化矽做為保護殼的情況下，能夠在最少阻擋電漿子效應的情況下得到17~20 %的元件增益，而外部量子效率量測也顯示電漿子效應與散射效應皆對此元件光電流增益有所貢獻。在第三部分中，本論文使用一個簡易濕式系統進行p-n接面的界面調整。實驗中將製備好的銅銦鎵硒吸收層浸泡至一含三氯化鎵以及硫代乙醯胺的混合溶液中數十秒，清洗後進行後續元件製程。實驗結果顯示此一潤浸動作能夠減少p-n接面的界面缺陷，提高載子生命周期，使元件效率能夠從1.02 %提升到6.40 %。第四部分中，本論文使用二氧化鈦-二氧化矽核殼結構做為銅銦鎵硒元件之抗反射層。此核殼結構之有效折射率近似於透明導電層折射率與空氣折射率的幾何平均數，能夠大幅減少入射光的反射率。此外，二氧化矽折射率也近似於二氧化鈦折射率與空氣折射率的幾何平均數，更能減緩入射光被反射的可能性。此一抗反射層透過增加元件光電流而有效提升元件效率，效率增益高達10.75 %。綜述以上四大實驗方向分別從減緩載子複合以及提高元件光吸收，進而成功提升元件表現，相信必能對太陽能產業的研究與發展有所貢獻。

Chalcopyrite photovoltaics (PVs) possesses the great potential for industrial application, and scientists put a lot of effort into the improvement of the cell performance. In the first part of this thesis, we have proposed the self-assembled Al2O3 nanostructure (Al2O3 NS) using glancing angle deposition system (GLAD) and placed it at the interface between Cu(In,Ga)Se2/Mo. The negative charge surrounding the Al2O3 NS repels the electrons, in turn reducing the recombination at the rear surface. In addition, the most striking observation is the alleviation of the phase-separated Cu(In,Ga)Se2 film. With the optimization of the Al2O3 NS, we observe a significant enhancement in cell performance, yielding a power conversion efficiency (PCE) increase from 2.83 to 5.33%.
In the second part of this thesis, we have presented the findings of the research focusing on the combination of plasmonic effect and chalcopyrite PVs. We incorporated gold nanoparticles (Au NPs) encapsulated by a thin protective SiO2 shell in the chalcopyrite absorber-based PVs deposited via solution deposition techniques. The surface plasmonic resonance (SPR) induced field and increased optical path generated by the nanoparticles result in a significant enhancement in light absorption, resulting in the enhanced PCE in solution-processed rigid CuIn(S,Se)2 from 1.95 to 2.35%, and flexible Cu(In,Ga)Se2 PVs from 9.28 to 10.88%.
In the third part of this thesis, we have demonstrated a facile wet soaking process by dipping a Cu(In,Ga)Se2 thin film in a mixed aqueous solution containing GaCl3 and thioacetamide (C2H5NS) at 80˚C for several seconds to modify the p-n junction. The less defective Zn(O,S)/ Cu(In,Ga)Se2 p-n junction are confirmed by both temperature-dependent open circuit voltage (VOC) and time-resolved photoluminescence (TRPL). Therefore, the cell performance can be improved after the wet and light soaking processes, exhibiting the enhanced PCE from 1.02 to 6.40%.
In the fourth part of this thesis, we have developed a novel TiO2-SiO2 core-shell nanostructure (TiO2@SiO2 NS) via GLAD and Stöber method for Cu(In,Ga)Se2 PVs. It begins by laying out the optical simulation of the anti-reflective coating (ARC) via finite-difference time-domain (FDTD) for parameters optimization, and the following device fabrication is based on the simulated results. The reduction of reflectance leads to improved light absorption across a broad wavelength range, improving the PCE from 6.32 to 7.00% after introducing the TiO2@SiO2 NS as the ARC for Cu(In,Ga)Se2 PVs.
This dissertation provides several important opportunities to break the bottleneck of chalcopyrite PVs, which is beneficial for future practice.

摘要 i
Abstract iii
誌謝 v
Table of contents vii
List of figures xi
List of tables xxi
List of abbreviations and symbols xxiii
Chapter 1 Introduction 1
Chapter 2 Literature Reviews 5
2.1 Cu(In,Ga)Se2 structure 6
2.1.1 Soda-lime glass (SLG) 6
2.1.2 Mo back electrode 6
2.1.3 Cu(In,Ga)Se2 absorber layer 7
2.1.4 Buffer layer 9
2.1.5 Window layer 10
2.1.6 Anti-reflective coating (ARC) 10
2.2 Motivations 11
2.2.1 Rear passivation techniques for ultra-thin Cu(In,Ga)Se2 TFPVs 11
2.2.2 Improved absorption via plasmonic nanoparticles 14
2.2.3 Modification of the p-n junction 15
2.2.4 Nanostructured anti-reflective coating for Cu(In,Ga)Se2 TFPVs 17
Chapter 3 Experimental Techniques 19
3.1 Cu(In,Ga)Se2 thin film preparation 19
3.2 Rear-passivated Cu(In,Ga)Se2 TFPVs 20
3.3 Plasmonic chalcopyrite TFPVs 21
3.3.1 Synthesis of Au@SiO2 nanoparticles 21
3.3.2 Fabrication of CuIn(S,Se)2 TFPVs on ridged substrates 22
3.3.3 Fabrication of Cu(In,Ga)Se2 TFPVs on flexible substrates 23
3.4 Modified p-n junction of the Cu(In,Ga)Se2 TFPVs 23
3.5 Nanostructured anti-reflective coating for Cu(In,Ga)Se2 TFPVs 24
3.6 Material characterization 24
3.7 Device characterization 25
3.8 Optical simulation 26
Chapter 4 Enhanced Performance of Cu(In,Ga)Se2 TFPVs with Nanostructured Al2O3 Passivation Layer 27
4.1 Preface 27
4.2 Results and discussion 28
4.2.1 Enhanced Cu(In,Ga)Se2 device performance with various coverages of Al2O3 NSs 28
4.2.2 Enhanced Cu(In,Ga)Se2 device performance with various thicknesses of Al2O3 NSs 36
4.2.3 Investigation of reduced recombination from the Al2O3 NS 43
4.3 Summary 48
Chapter 5 Enhanced Cell Efficiency in Solution-Processed Chalcopyrite TFPVs Utilizing Plasmonic Au@SiO2 NPs 50
5.1 Preface 50
5.2 Results and discussion 51
5.2.1 Plasmonic enhanced Au@SiO2-CuIn(S,Se)2 TFPVs on rigid substrates 51
5.2.2 Plasmonic enhanced Au@SiO2-Cu(In,Ga)Se2 devices on flexible substrates 61
5.3 Summary 63
Chapter 6 Enhanced Solar Performance of CBD-Zn(O,S)/Cu(In,Ga)Se2 TFPVs via Interface Engineering by Wet Soaking Process 65
6.1 Preface 65
6.2 Results and discussion 66
6.2.1 Material characterization 66
6.2.2 Device characterization 69
6.3 Summary 75
Chapter 7 Design of Novel TiO2@SiO2 Helical Nanostructured Anti-Reflective Coatings on Cu(In,Ga)Se2 TFPVs with Enhanced Cell Performance 76
7.1 Preface 76
7.2 Results and discussion 77
7.2.1 Optical simulation 78
7.2.2 Material characterization 82
7.2.3 Device characterization 85
7.3 Summary 90
Chapter 8 Conclusions 92
Reference 95

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