我們使用較低溫且環保的方式在水相中合成硫化鎘奈米晶體，利用粉末式X射線繞射分析發現硫化鎘奈米晶體具有相轉換情形的發生。其結構可由六方晶系轉換成立方晶系，並深入探討在含有鹵素離子及酸濃度改變情況下其相轉換程度。之後成功合成出尺寸可調控的菱形十二面體硫化鎘奈米粒子，尺寸範圍介於64奈米至150奈米之間。在粉末式X射線繞射分析中，得知其具有面心立方晶系。硫化鎘菱形十二面體在掃描式電子顯微鏡及穿透式電子顯微鏡的觀察下，其形狀邊角完整且表面平滑。此外，在選區繞射圖，我們可以再次驗證合成出來的奈米粒子為具有{110}單一晶面的硫化鎘晶體。在紫外光可見光漫反射光譜圖中，可以觀察到硫化鎘菱形十二面體在光學上有尺寸效應，硫化鎘菱形十二面體的能隙會隨著尺寸增加而有微略紅位移的現象。相比於大顆的硫化鎘菱形十二面體，尺寸為64奈米的硫化鎘菱形十二面體擁有較大的活性表面積。

We have synthesized CdS nanocrystals at relatively low temperatures in aqueous solutions. From XRD analysis, we can observe a crystal phase transformation from a hexagonal wurtzite phase to a cubic zinc blende phase by tuning halide ions and pH values. Size-tunable CdS rhombic doecahedra (RDs) ranging from 64 nm to 150 nm have been synthesized and identified through XRD to have face-centered cubic lattices. They have sharp edges and smooth surfaces. SAED patterns indicate that the synthesized CdS RDs are bound by the {110} facets. UV–vis DRS results reveal that the CdS RDs still show size-dependent optical properties. The band gap of CdS RDs is slightly red-shifted as the size of CdS nanoparticles increase. Compared to bigger CdS RDs, the 64 nm CdS RDs have a larger active surface area.

論文摘要 I
Abstract II
Acknowledgement III
Table of Contents IV
List of Figures VIII
List of Schemes XIV
List of Table XV
1.Introduction 1
1.1 Size- and Facet-Dependent Properties of Semiconductor Crystals 1
1.1.1 Facet-Dependent Electrical Conductivity Properties of Semiconductors 1
1.1.2 Facet- and Size-Dependent Optical Properties of Semiconductors 6
1.2 Cadmium Sulfide (CdS) 10
1.2.1 Structural Transformation of Cadmium Sulfide from Zinc Blende to Wurtzite 10
1.2.2 Synthesis of CdS Nanoparticles in Organic Solutions 13
1.2.3 Synthesis of CdS Nanoparticles in Aqueous Solutions 17
Motivation 21
2 Experimental Section 22
2.1 Chemicals 22
2.2 Synthesis of CdS Nanoparticles by Changing the Cadmium Precursor and Acid 22
2.3 Multiple Methods to Synthesize CdS Nanoparticles with a Specific Structure 24
2.3.1 Halide-Induced Structural Control in CdS Nanoparticles 25
2.3.2 Synthesis of CdS Nanoparticles with CTA+ and Halide Ions 26
2.4 Synthesis of Wurtzite to Zinc Blende CdS Nanoparticles by Adjusting the Nitric Acid Amount 26
2.5 Synthesis of Zinc Blende Structured CdS Nanoparticles by Controlling the Heating Temperature 28
2.6 Growth of Size-Tunable CdS Rhombic Dodecahedra 29
2.7 Electrical Conductivity Measurements 30
2.8 Electrochemical Measurements 30
3 Instrumentation 33
4 Results and Discussion 35
4.1 CdS Nanoparticles by Changing Different Cadmium Precursors and Acids 36
4.2 Halide-Induced Structural Control and Formation Mechanism of CdS Nanoparticles 39
4.2.1 Structural Control of CdS Nanoparticles with Halide Ions 39
4.2.2 Hypothesized Formation Mechanism of CdS Nanoparticles with Halide Ions 44
4.3 Acid-Induced Structural Transformation of CdS Nanoparticles 47
4.4 CdS Rhombic Dodecahedra with a Zinc-Blende Structure 53
4.4.1 Growth of CdS Rhombic Dodecahedra 53
4.4.2 Characterization of Size-Tunable CdS Rhombic Dodecahedra. 57
4.4.3 Optical Size Effects of CdS Rhombic Dodecahedra 61
4.5 Electrochemistry Analysis of CdS Rhombic Dodecahedra 66
4.5.1 Mott‒Schottky Plots of Conduction Band Position 66
4.5.2 Electrochemical Surface Area (ECSA) and Transient Photocurrent Response 70
5 Conclusion 73
References 74

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