指導教授：劉如熹臺灣大學：化學研究所莊博翔Chuang, Po-HsiangPo-HsiangChuang2014-11-252018-07-102014-11-252018-07-102014http://ntur.lib.ntu.edu.tw//handle/246246/261306奈米等級尺寸之半導體量子點能階可隨粒徑大小與成分組成改變，其具有獨特之光學特性。然而過去以鎘(Cd)為主之量子點具有毒性，使其發展受到限制。因此，本篇論文研究重點為研發無毒量子點與其應用，此些量子點包含硫化銅銦 (CuInS2;CIS)與磷化銦(InP)。首先，我們利用簡易水熱合成法合成出於不同反應時間之CuInS2量子點。經由硫化鋅(ZnS)包覆於CIS外層形成CIS/ZnS核殼(Core/shell)結構，可增強其放光量子效率至84%。CIS/ZnS具有高量子效率與較大之半高寬。因此，使用此無毒量子點為發光二極體應用於照明為良好之光轉換發光材料。我們加入紅光CIS/ZnS量子點至白光發光二極體裝置內，可改善色彩演色指數至86 (Ra = 86)。我們進一步水熱合成法合成出不同銅(Cu)與銦(In)比例之與CIS量子點。隨銅含量減少，可系統性調控CIS之能階使其變寬。藉由ZnS包覆CIS形成CIS/ZnS量子點，因不同銅含量可調控波段與增強其量子效率。我們進一步研究CIS與CIS/ZnS量子點之光學特性，晶體結構變化與熱穩定性探討。高效率CIS/ZnS量子點與綠色螢光粉Ba2SiO4:Eu2+與藍光發光二極體結合之裝置於色彩演色指數可達近90(Ra = 90)。同時，CIS/ZnS量子點封裝於電激發光之發光二極體元件具有良好潛力。我們也合成InP與InP/ZnS量子點，並分析與探討其與InP量子點當作牙科樹酯之發光來源與混合後之放光特性。觀測InP量子點當作牙科樹酯混合材料對於人類牙齦造纖維母細胞之生物毒性量測。由結果可得知其具良好生物相容性之牙科樹酯材料。Semiconductor quantum dots (QDs), whose particle sizes are in the nanometer range, have very unusual optical properties that depend upon the particle size and composition. However, in case of Cadmium-based QDs, Cd is toxic element, which would cause serious restrictions. Therefore, our researches focused on developing non-toxic QDs, which include CuInS2 and InP QDs and their applications. First, we synthesized CuInS2 (CIS) I-III-VI type quantum dots (QDs) under different growth times by the facile solvothermal method. The quantum yield (QY) can be enhanced to 85% by coating ZnS shell at outside of CIS, forming the CIS/ZnS core/shell QDs. CIS/ZnS QDs, show high efficiency and large full width at half-maximum (FWHM). Thus, these non-toxic QDs as light-emitting diodes (LEDs) converters for illumination are a good candidate. We also incorporated red emitting CIS/ZnS QDs into the fabricated white LEDs to improve the color rendering index (CRI) value (Ra = 86). We further synthesized CIS QDs with various [Cu]/[In] ratio by solvothermal method. The band gap and emission energies of CIS QDs are found to be systematically increased with decreasing Cu content. ZnS shell coated of CIS/ZnS core/shell QDs emit quite tunable wavelengths with high QY, depending on the composition. We further investigated the optical properties, lattice structure and thermal stability of CIS and CIS/ZnS core/shell QDs. By combining with high QY CIS/ZnS core/shell QDs as color converters with blue-emitting LEDs and green phosphors Ba2SiO4:Eu2+, the QDs-assisted LEDs with high CRI of near 90 are fabricated. Meanwhile, The potential to use CuInS2/ZnS QDs in LEDs is demonstrated by fabricating electroluminescent devices. We synthesized InP and InP/ZnS QDs and characterized the fluorescence. Additionally, dental resins containing InP QDs as luminophores and in vitro cytotoxicity of InP QDs-embedded resin was investigated by employing human gingival fibroblast cell, showing it’s a good biocompatible for dental material.Contents 摘要 III Abstract IV Chapter 1. Introduction 1 1.1 Nanomaterials 1 1.2 Principle of Semiconducting Quantum Dots (QDs) 2 1.2.1 Quantum Confinement Effect 3 1.2.2 Theory of Nucleation and Growth 6 1.2.4 Introduction of II-VI, III-V, and I-III-VI Semiconducting QDs 12 1.2.5 Luminescence Properties 20 1.2.6 Quantum Yield of QDs 21 1.3 Application of QDs 23 1.3.1 QDs as LEDs Wavelength Converters 23 1.3.2 Application for Electroluminescence (EL) Device 26 1.3.3 QDs in Dye-sensitized Solar Cell (DSSC) Device 30 1.3.4 Application of Bioimaging 31 1.4 Research Motivation 33 References (Chapter 1) 37 Chapter 2. Synthetic and Characterization Techniques 54 2.1 Materials 54 2.2 Syntheses of the Quantum Dots 56 2.2.1 Fabrication of InP Quantum Dots 56 2.2.2 Fabrication of InP/ZnS Quantum Dots 57 2.2.4 Fabrication of CuInS2/ZnS Quantum Dots with [Cu]/[In]=1/4 59 2.2.5 Fabrication of CuInS2 Quantum Dots with [Cu]/[In] = 1/1, 1/2, 1/4 and 1/6 60 2.2.6 Fabrication of CuInS2/ZnS Quantum Dots with [Cu]/[In] = 1/1, 1/2, 1/4 and 1/6 61 2.3 The Instruments for Characterization 63 2.3.1 Photoluminescence 63 2.3.3 Optical Quantities of Light-Emitting Diodes 65 2.3.4 Ultraviolet-visible (UV- Vis) Spectrophotometer 68 2.3.5 Transmission Electron Microscopy (TEM) 71 2.3.6 X-ray Diffraction 74 2.3.7 X-ray Photoelectron Spectroscopy (XPS) 77 Reference (Chapter 2) 79 Chapter 3. Enhancing the Color Rendering Index for Phosphor-converted White LEDs Using Cadmium-Free CuInS2/ZnS QDs 80 3.1 Introduction 80 3.2 Experimental Section 82 3.2.1 Materials 82 3.2.2 Synthesis of CuInS2 Cores and CuInS2/ZnS Core/Shell QDs 82 3.2.3 Fabrication of CIS/ZnS QD-assisted YAG:Ce Phosphor-based White LEDs 82 3.2.4 Characterization 83 3.3 Results and Discussion 84 3.4 Summary 91 References (Chapter 3) 92 Chapter 4. Emission tunable CuInS2/ZnS Quantum Dots by Tuning Cu/In ratio: Structure, Optical properties and Application to White Light-emitting Diodes 96 4.1 Introduction 96 4.2 Experimental Section 99 4.2.1 Materials 99 4.2.2 Synthesis of CuInS2 Cores and CuInS2/ZnS Core/Shell QDs 99 4.2.3 Fabrication of CIS/ZnS QD-assisted YAG:Ce Phosphor-based White LEDs 100 4.2.4 Fabrication of QD-LED device 100 4.2.5 Characterizations 101 4.3 Results and discussion 102 4.4 Summary 119 References (Chapter 4) 120 Chapter 5. Facile Dental Resin Composites with Tunable Fluorescence by Tailoring a Cd-free Composition Quantum Dots 128 5.1 Introduction 128 5.2 Experimental Section 130 5.2.1 Materials 130 5.2.2 Synthesis of InP QDs 130 5.2.3 Synthesis of InP/ZnS QDs 131 5.2.5 Preparation of InP QDs-embedded Resin 132 5.2.6 Cytotoxicity assay 133 5.2.7 Reactive Oxygen Species (ROS) Assay 134 5.2.7 Characterizations 134 5.3 Results and Discussion 135 5.4 Summary 148 References (Chapter 5) 149 Chapter 6. Concluding Remarks and Perspective 1537771425 bytesapplication/pdf論文公開時間：2016/07/16論文使用權限：同意無償授權無鎘量子點thesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/261306/1/ntu-103-D99223115-1.pdf