螢光奈米材料的製備及其於太陽能電池與生物感測器之應用

螢光奈米材料由於其獨特之光學特性如尺寸量化的放光、較窄的放射波帶、與光穩定性的關係，使其於生物感測與太陽能電池的應用是很有趣的。本篇論文主要著重於水相半導體奈米粒子(quantum dots, QDs)與螢光金屬奈米團簇(nanoclusters, NCs)的製備、鑑定及應用。首先利用光輔助方式合成高量子產率且窄放光波帶之硒化鋅(硫) (ZnSe(S))量子點。利用類似之光輔助合成法製備高水溶性之含汞硒化鋅量子點(ZnxHg1–xSeyS1–y QDs)，放光波長從可見光藍光(blue)位置調控至近紅外光(Near-infrared)的範圍。我們利用螢光光譜(PL spectra)、高解析穿透式電子顯微鏡(HR-TEM)、X-光粉末繞射儀(XRD)、X-光光電子能譜儀(XPS)鑑定這些奈米材料。利用熱控制方法長成不同粒徑之碲化鎘量子點有效增加所製備之量子點敏化太陽能電池的能量轉換效率(η = 2.02%)。我們藉由特定單股去氧核糖核酸(DNA)，以硼氫化鈉(NaBH4)還原銀、銅離子製備成高螢光效率、生物可容之銅/銀奈米團簇。利用電噴灑質譜法(ESI-MS)、感應耦合電漿質譜分析儀(ICP-MS)決定此螢光銅/銀奈米團簇由一個銅與兩個銀原子所組成；相較於銀奈米團簇，銅/銀奈米團簇具備較佳之量子產率(QY, 51.2% vs. 11.5%)且所需合成時間更短(1.5 h vs. 120 h)。根據銅離子所造成螢光提升之現象，我們利用此螢光銀奈米團簇作為探針，發展一種免標定(label-free)、螢光增強(turn-on)、勻相分析系統；可靈敏(偵測極限: 8 nM)且選擇性(> 350倍對Pd2+)偵測銅離子。我們亦設計一段單股DNA序列，結合聚合胞嘧啶(C12)與特定辨識延胡索醯乙醯乙酸水解酶(fumarylacetoacetate hydrolase)之序列合成功能性之銀奈米團簇。此功能性銀奈米團簇具有良好的靈敏性(偵測極限: 14 nM)且可選擇性分辨單點突變 (single-base mismatch)之序列。

關鍵字

量子點；光輔助合成法；量子點敏化太陽能電池；螢光銀(銅/銀)奈米團簇；銅離子；單股去氧核糖核酸偵測；單一核苷酸多型態

並列摘要

Fluorescent nanomaterials are interesting for use in bioassays and solar cells, mainly because of their unique optical properties, including size-dependent emission wavelengths, narrow emission profiles, and photostability. This thesis focuses on preparation, characterization, and applications of water soluble semiconductor quantum dots (QDs) and fluorescent metallic nanoclusters (NCs). I developed a photo-assisted approach for the synthesis of ZnSe(S) QDs that fluoresce strongly and exhibit a narrow bandwidth. A photo-assisted method was applied to the synthesis of highly-water soluble ZnxHg1–xSeyS1–y QDs having emission ranging from blue to near-infrared (NIR) region. PL spectra, high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) and/or X-ray photoelectron spectroscopy (XPS) were used to characterize the as-prepared nanomaterials. I also developed a simple heating approach to prepare various sizes of CdTe QDs, leading to increased energy conversion efficiency (2.02%) of QDSSCs. A simple and rapid approach was demonstrated for the preparation of highly fluorescent and biocompatible DNA-Cu/Ag NCs from AgNO3, Cu(NO3)2, and NaBH4 using single-strand DNA scaffolds. Electrospray ionization mass spectrometry (ESI-MS) and inductively coupled plasma mass spectrometry (ICP-MS) were employed to characterize the DNA-Cu/Ag NCs, revealing that each DNA-Cu/Ag NC contain two Ag and one Cu atoms. The DNA-Cu/Ag NCs provided great fluorescence (QY 51.2%). Based on the fact that Cu2+ ions induced fluorescence enhancement of the DNA-Ag NCs, I further developed a label-free, fluorescence turn-on, and homogeneous assay for the highly selective and sensitive (8 nM) detection of Cu2+ ions. I also used a specific DNA scaffold consisting of a fluorescent-based motif (C12) and a specific sequence (CCAGATACTCACCGG) that recognizes a gene of fumarylacetoacetate hydrolase to prepare functional DNA-stabilized Ag NCs. The as-prepared DNA-stabilized Ag NCs exhibited good sensitivity (14 nM) and selectivity against a single-base mismatch (DNAmmt) sequence.

並列關鍵字

quantum dots ； photo-assisted method ； quantum dot-sensitized solar cell ； fluorescent Ag(Cu/Ag) nanoclusters (NCs) ； copper ions ； DNA detection ； single nucleotide polymorphisms (SNPs)

參考文獻

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螢光奈米材料的製備及其於太陽能電池與生物感測器之應用

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