臺灣博碩士論文加值系統

在本論文中，將探討三個奈米材料用於電子元特性相關的主題。利用奈米材料本身設計，奈米材料外部結構設計，以及製程處理的方式，使之充分與電子元件結合，發揮其特長，增加元件效率。第一個主題是在氧化鋅奈米針狀結構中，利用材料表面次波長結構的設計引發光捕捉現象，藉此提高了奈米材料的光電特性。我們把氧化鋅(ZnO)通過整合串接GaInP/GaAs/Ge太陽能電池作為抗反射層，搭配聚光系統，提升串接電池的光電轉換效率提高為原本的45.8%，並直接於戶外測試，針對奈米材料的全角度抗反射特性，成功結合串接型電池應用。第二個主題是利用特殊的奈米珊瑚形狀ZnO用於光激發的室溫氣體感測器，提升感測靈敏度，量測氣體為甲苯。由於奈米材料高表面積比，用於提升氣體感測材料接觸為常見課題，但我們發現藉由特殊的構型設計結合微弱紫外光激發(強度 2μw/cm2)，能提升元件的效率，利用特殊的珊瑚奈米結構我們可以將元件的感測敏感度增強為原本的1022%。第三主題是開發二硫化鉬 (MoS2)此二維材料的氣體感測器，並提出元件的感測靈敏度理論模型，提升MoS2氣體感測器效率方法。二維材料中最熱門的MoS2，可作為適溫的氣體感測材料，由於MoS2在生成之後常帶有缺陷，我們發現適當的缺陷有助於幫助提升氣體感測器的量測敏感度，藉由最佳參數，量測氣體為甲醇，我們實現氣體感測器大於500% (從5%提升到27.2%)敏感度的提升，並大幅降低氣體的濃度量測範圍(從2000 ppm下降到 100 ppm)。這工作實現了解釋單層二維材料與氣體感測機制上的探討。我們預期這個工作將對未來二維材料設計及發展有重要影響。

Particular physical and chemical properties of nanomaterials have promised and exhibited great applications in manufacturing various nanodevices such as electron field emitters, sensors, photovoltaics and other electronic components. In this thesis, I will experimentally explore three topics which realize the improvement of solar cells and gas sensors. The first topic is that ZnO nanostructure as an anti-reflectance coating for commercial GaInP/GaAs/Ge triple-junction solar cells. Covered by the unique tapered nanoneedles, the efficiency of the tandem solar cell coated with the ZnO nanoneedles is effectively improved 45.8 % higher than that with bare surface. The excellent omnidirectionality and heat sustainability demonstrated here bring promising potential for multi-junction concentrator solar cells. The second topic is a simple and low cost hydrothermal process was adopted to synthesize corals-like ZnO for gas sensors applications. Toluene was detected with the photoactivated gas detector by 2μW/cm2 ultraviolet (UV) illumination. Giant sensitivity enhancement of the detector is due to the high surface area/volume ratio morphology of corals-like ZnO nanorod arrays (NRAs) and photoinduced oxygen ions increasing by UV illumination. The corresponding sensitivity (ΔR/R0) of ZnO corals-like NRAs based detector was approximately enhanced 1022 % than ZnO thin film sensors. The third topic is about two-dimensional (2D) nanomaterials atomic MoS2 gas sensors. A highly sensitive gas sensor based on the chemical vapor deposition synthesized MoS2 was developed. The target gas was methanol. We demonstrated the highly enhanced performance of atomic trilayer MoS2 gas sensor by oxygen plasma treatment. During the plasma treatment 40s, the response of MoS2 gas sensor is more 500 % higher than original MoS2 (from 5% to 27.2%) and increase the limit of detection from 2000 ppm to 100 ppm. Photoluminescence (PL) clearly reveals the number of defects which contribute the ability of gas adsorption. This result can improve the device performance which has the same mechanism of 2D nanomaterials.

Contents
口試委員會審定書……………………………………………………………..……... i
誌謝………………………………………………………………..………………...…ii
中文摘要…………………………………………………………………………...….iii
Abstract…………………………………………………………………………..….....iv
List of Figures…………………………………………………………………………..7
List of Tables…………………………………………………………………………..12
Chapter 1 Introduction………………………………………………………………..13
1.1. One-Dimensional (1D) and Two-Dimensional (2D) Nanomaterials…….……….13
1.1.1. 1D Materials…………………………………………………………..…...13
1.1.2. 2D Materials………………………………………………………………15
1.1.3. 1D and 2D Materials Overview………………………..…………….........16
1.2. Various Synthesis Methods of 1D and 2D Nanomaterials………………………..18
1.2.1. Physical Methods………………………………………………………….....19
1.2.1.1. Evaporation Technique………………………………………………….19
1.2.1.2. Sputtering Technique……………………………………………………20
1.2.1.3. Lithography Processes………………………………………………......21
1.2.1.4. Hot and Cold Plasma……………………………………………….…...21
1.2.1.5. Spray Pyrolysis………………………………………………………….23
1.2.1.6. Inert Gas Phase Condensation Technique……………………………….24
1.2.1.7. Pulsed Laser Ablation…………………………………………………...25
1.2.1.8. Sonochemical Reduction………………………………………………..26
1.2.2. Chemical Methods…………………………………………………………...28
1.2.2.1. Lyotropic Liquid Crystal Templates…………………………………….28
1.2.2.2. Electrochemical Deposition……………………………………………..29
1.2.2.3. Electroless Deposition…………………………………………………..30
1.2.2.4. Hydrothermal Techniques……………………………………………….31
1.2.2.5. Sol–gel technique………………………………………………………..32
1.2.2.6. Chemical Vapor Deposition……………………………………………..33
1.2.2.7. Laser chemical vapor deposition technique (LCVD)…………………...34
1.2.2.8. Laser Pyrolysis…………………………………………………………..34
1.3 Current Syntheses of 1D and 2D Nanomaterials………………………………….36
1.3.1. Synthesis of 1D Nanomaterial…………………………………………….36
1.3.1.1. Synthesis of 1D ZnO Nanomaterials………………………………36
1.3.2. Synthesis of 2D Nanomaterial…………………………………………….40
1.3.2.1. Synthesis of 2D MoS2 Nanomaterials……………………………...40
1.4. Nanomaterials for Solar Cells and Gas Sensors Applications……………………43
1.4.1. Current Status of 1D Materials for Solar Cells……………………………44
1.4.2. Current Status of 1D Materials for Gas Sensors…………………………..48
1.4.3. Current Status of 2D Materials for Gas Sensors…………………………..53
1.5. Research Motivation……………………………………………………………...58
1.5.1. Enhancement of Photovoltaic Conversion Efficiency with Omnidirectional Antireflection Coatings…………………………………………………..............58
1.5.2. High Enhancement Sensitivity of Gas Sensors without Heating………….59
1.5.3. Classification of Sensing Mechanism for the Novel Gas Sensors Using 2D Materials…………………………………………………………………………60
1.6. Thesis Structures………………………………………………………………….61

Chapter 2 Preparing, Fabrication, and Characterization of ZnO and MoS2 Nanomaterials for Applications……………………………………..………………...62
2.1. Hydrothermal Methods of ZnO Various Nanostructures…………………………62
2.1.1. Theory……………………………………………………………………..62
2.1.2. Fabrication Process………………………………………………………..63
2.1.3. Characterization……………………………………………………...........66
2.2. Synthesis of Atomic Layers MoS2 by CVD Methods…………………………….69
2.2.1. Theory……………………………………………………………………..69
2.2.2. Fabrication Process………………………………………………………..69
2.2.3. Characterization……………………………………………………...........71

Chapter 3 ZnO and MoS2 Nanomaterials Integrating with Solar Cells and Gas Sensors Technology…………………………………………………………….………………74
3.1. Theory…………………………………………………………………………….74
3.1.1. Solar Cells…………………………………………………………………74
3.1.1.1. The Factors Affecting the Performance of Solar Cells…………….74
3.1.1.2. Muti-Junction Solar Cells………………………………………….75
3.1.1.3. Concentrating Photovoltaic (CPV)………………………………...75
3.1.1.4. Nanostructures as Antireflection Layers…………………………...76
3.1.1.5. Haze and Light-Tarping in Photovoltaic Conversion Efficiency…..77
3.1.2 Gas Sensors………………………………………………………………...77
3.1.2.1. The Factors Affecting the Performance of Gas Sensors…………...77
3.1.2.2. Gas Sensing Mechanism and UV Effects………………………….78
3.1.2.3. Surface-to-Volume Ratio…………………………………………..81
3.1.2.4. Carrier Transferring Efficiency…………………………………….82
3.2 Process Integration………………………………………………………………...84
3.2.1 Solar Cells………………………………………………………………….84
3.2.2 Gas Sensors………………………………………………………………...85
3.3 Experimental Set Up………………………………………………………………89
3.3.1 Solar Cells………………………………………………………………….89
3.3.2 Gas Sensors……………………………………………………………..….90

Chapter 4 Results and Discussions for ZnO and MoS2 Nanomaterials Integrating with Solar Cells and Gas Sensors…………………………………………………………..93
4.1. Various ZnO nanostructures as Antireflection Coatings for Multi-Junction Solar Cells…………………………………………………………………………………...93
4.1.1. Overview…………………………………………………………..………93
4.1.2. Results and Discussion……………………………………………………95
4.1.3. Summary…………………………………………………………………109
4.2 Performance and Characterization of Nanostructured ZnO Gas Sensors………..110
4.2.1. Overview…………………………………………………………………111
4.2.2. Results and Discussion…………………………………………………...111
4.2.3 Summary………………………………………………………………….122
4.3 Performance and Characterization of Atomic Layers MoS2 Gas Senors………...123
4.3.1Overview…………………………………………………………….. …...123
4.3.2 Results and Discussion…………………………………………………...124
4.3.3 Summary………………………………………………………………….130
Chapter 5 Conclusion………………………………………………………………..131
Chapter 6 Future Prospects…………………………………………………………..134
Reference…………………………………………………………………………….136

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