The synthesis of n-alkylamine-bound CdSe-NH2Rʹ nanocrystals from carboxylateterminated CdSe-Cd(O2CR)2/HO2CR requires the removal of acidic impurities prior to the addition of primary amine. Otherwise, the formation and subsequent tight binding of n-alkylammonium carboxylate ion pairs prevents quantitative removal of carboxylate species. Dimethylcadmium and diethylzinc were used as reagents to deprotonate acidic impurities, which either causes methylation (with a surface density of 0.04−0.22 nm−2) and photoinduced reduction of the nanocrystal core or X-type ligand exchange with ethyl species, respectively. The acid-scavenged nanocrystals could be completely isolated from displaced carboxylate ligands (≤ 0.01 carboxylates nm-2). In addition to traditional selective precipitation procedures, gel permeation and silica chromatography were investigated as alternative purification methods for the isolation of CdSe-NH2Rʹ. Both demonstrated no improvement compared to the more convenient precipitation process. Thin films fabricated from CdSe-NH2C4H9 show little to no grain growth upon thermal annealing at 250 ºC, maintaining domains (~10 nm) despite complete desorption of n-butylamine from the nanocrystal surface above 150 ºC. Despite no passivation of the surface and a high density of grain boundaries, thin film transistors of CdSe-NH2C4H9 fabricated on thermally grown silicon dioxide gate dielectrics produce field-effect transistors with an average electron mobility of 12 ± 1 cm2 V-1s-1, a low threshold voltage hysteresis (4.0 ± 0.6 Vth), and an on/off ratio of 8x104. Colloidal dispersions of amine bound nanocrystals (CdSe−NH2Rʹ) are indefinitely stable at amine concentrations of 0.1 M or higher and slowly aggregate at lower concentrations. Dissociation and evaporation of the amine ligands in 4-ethylpyridine, tri-n-butylphosphine, or molten tri-n-octylphosphine oxide solution results in nanocrystal aggregation. Greater stability can be achieved using dimethyl-n-octadecylphosphine as the L-type ligand, yielding soluble CdSe- PMe2C18H37 nanocrystals with a phosphine coverage of 1.8 nm-2. CdSe-PMe2C18H37 is the first stable nanocrystal sample bound solely by neutral phosphines. Z-type rebinding was investigated with metal oleate species (Mn+(O2CR)n, M = Cd2+, Zn2+, Pb2+, In3+), and a relative binding affinity of these complexes can be established. Rebinding of metal oleate species at 25 ºC yield lower coverages, yet can reach saturation upon heating to 100 ºC. The rebinding of cadmium chloride to aggregated CdSe-PBu3 stabilizes the particle and aids in their redissolution. L-type ligand exchange and subsequent Z-type rebinding was employed towards the synthesis of a new model compound passivated by dimethyl-n-octadecylphosphine and cadmium trifluoroacetate ligands, CdSe-Cd(O2CCF3)2/PMe2C18H37, which is characterized by UV-Vis, 1H, 19F, and 31P NMR spectroscopies. The findings of this dissertation demonstrate the importance of ion-pair species in the colloidal stabilization of colloidal nanocrystal systems. It also indicates the utility of stoichiometric, amine and phosphine-bound CdSe-L to act as both reporter complexes and as a clean reactive reagent for synthesis of novel CdSe-MX2/L systems to study the molecular interactions at nanocrystal surfaces.

Lam, Ngai Sze. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references. / Text in English; abstracts in English and Chinese. / Lam, Ngai Sze. / Abstract --- p.i / Acknowledgements --- p.iii / Table of contents --- p.iv / List of Figures --- p.viii / List of Tables --- p.xiii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Background --- p.1 / Chapter 1.1.1 --- Properties of CdSe --- p.1 / Chapter 1.1.2 --- Synthesis of CdSe one-dimensional (ID) nanostructure --- p.5 / Chapter 1.1.3 --- Application of CdSe nanostructures --- p.8 / Chapter 1.1.4 --- Significance of surface engineering --- p.10 / Chapter 1.1.4.1 --- Surface passivation --- p.11 / Chapter 1.1.4.2 --- Surface functionalization --- p.11 / Chapter 1.1.4.3 --- Modulation of optical/electrical properties --- p.12 / Chapter 1.2 --- Present study --- p.14 / Chapter 1.2.1 --- Objective --- p.14 / Chapter 1.2.2 --- General methodology --- p.14 / Chapter Chapter 2 --- Instrumentation --- p.19 / Chapter 2.1 --- Introduction --- p.19 / Chapter 2.2 --- Setup of Sample Preparation --- p.19 / Chapter 2.2.1 --- Synthesis --- p.19 / Chapter 2.2.1.1 --- Thermal evaporation apparatus --- p.19 / Chapter 2.2.1.2 --- Microwave assisted chemical synthesis --- p.21 / Chapter 2.2.2 --- Sample handling --- p.22 / Chapter 2.2.3 --- Other treatments --- p.22 / Chapter 2.3 --- X-ray photoelectron spectrometer (XPS) --- p.22 / Chapter 2.3.1 --- Basic Principle --- p.22 / Chapter 2.3.2 --- Instrumentation --- p.24 / Chapter 2.3.3 --- Charging problem --- p.27 / Chapter 2.3.4 --- Qualitative analysis --- p.27 / Chapter 2.3.5 --- Quantitative analysis --- p.28 / Chapter 2.3.5.1 --- Curve fitting --- p.28 / Chapter 2.3.5.2 --- Atomic percentage --- p.29 / Chapter 2.3.5.3 --- Thickness determination --- p.29 / Chapter 2.4 --- Photoluminescence --- p.30 / Chapter 2.4.1 --- Basic principle --- p.30 / Chapter 2.4.2 --- Instrumentation --- p.31 / Chapter 2.5 --- Other equipments --- p.32 / Chapter Chapter 3 --- Synthesis of CdSe Nanorods --- p.34 / Chapter 3.1 --- Introduction --- p.34 / Chapter 3.2 --- Thermal evaporation --- p.34 / Chapter 3.2.1 --- Experimental procedures --- p.34 / Chapter 3.2.2 --- Characterization --- p.35 / Chapter 3.3 --- Microwave assisted method --- p.41 / Chapter 3.3.1 --- Experimental procedures --- p.41 / Chapter 3.3.2 --- Characterization --- p.42 / Chapter 3.4 --- Summary --- p.47 / Chapter Chapter 4 --- Surface Treatment of CdSe Nanorods --- p.49 / Chapter 4.1 --- Introduction --- p.49 / Chapter 4.2 --- Experimental procedures --- p.50 / Chapter 4.3 --- Results and Discussion --- p.51 / Chapter 4.3.1 --- Formation of Se-coated CdSe NRs --- p.51 / Chapter 4.3.2 --- Desorption and thinning --- p.56 / Chapter 4.3.3 --- Surface degradation --- p.67 / Chapter 4.4 --- Summary --- p.69 / Chapter Chapter 5 --- Surface Capping of CdSe Nanorods --- p.73 / Chapter 5.1 --- Introduction --- p.73 / Chapter 5.2 --- Experimental procedures --- p.73 / Chapter 5.3 --- Results and Discussion --- p.74 / Chapter 5.3.1 --- Capping of thiol with halo-functional group --- p.74 / Chapter 5.3.1.1 --- Compositional analysis --- p.75 / Chapter 5.3.1.2 --- PL analysis --- p.79 / Chapter 5.3.2 --- Capping of DNA --- p.81 / Chapter 5.3.2.1 --- Compositional analysis --- p.81 / Chapter 5.3.2.2 --- PL analysis --- p.83 / Chapter 5.4 --- Summary --- p.92 / Chapter Chapter 6 --- Conclusions and Future Work --- p.94 / Chapter 6.1 --- Conclusions --- p.94 / Chapter 6.2 --- Future work --- p.95

Titanium dioxide (TiO2) photocatalysis, which can oxidise or reduce organic and inorganic pollutants, is a developing technology for water and wastewater treatment. The current work investigates the photocatalytic reduction of cadmium and selenium species as the presence of these elements in water are of environmental concern. Although TiO2 has been widely used for the photocatalytic process, its light absorption is limited to the UV region of the solar spectrum. Hence, the current project also explores the possibility to deposit cadmium selenide (CdSe) onto TiO2 to extend the photoresponse to the visible region. This study demonstrated that cadmium (Cd(II)) could be reduced to its metallic form by photocatalysis. The choice of hole scavengers and reaction pH are of importance in determining whether the photocatalytic reduction reaction will occur. It is also essential that both Cd(II) and organic additives are adsorbed on the surface of TiO2. A mechanism for cadmium photoreduction in the presence of formate as the hole scavenger was proposed. The current investigation elucidated the mechanism for the photoreduction of selenite (Se(IV)). Selenite was found to be photoreduced to its elemental form (Se(0)) as films, by direct photoreduction of Se(IV), and as discrete particles, by the reaction between Se(IV) and selenide (Se(2-)) ions. The Se(2-) ions are believed to have been generated from the 6 electron photoreduction of Se(IV) and/or the further photoreduction of the Se(0) deposits. Photocatalytic reduction reactions of Se(IV) and selenate (Se(VI)) using different commercial TiO2 materials was also studied. The current work also successfully deposited CdSe by photocatalysis using Se-TiO2 obtained from the photoreduction of Se(IV) and Se(VI). The mechanism for CdSe deposition was clarified and attributed to the reaction of Cd(II) present in the system and the Se(2-) released from the reduction of Se(0) upon further illumination. The Se??TiO2 photocatalysts obtained from the photoreduction of different selenium precursors (Se(IV) and Se(VI)) resulted in the dominance of different morphologies of the CdSe particles. This suggests a new approach to manipulate the properties of CdSe during its formation, and hence control over electrical and optical properties of this semiconductor.

Titanium dioxide (TiO2) photocatalysis, which can oxidise or reduce organic and inorganic pollutants, is a developing technology for water and wastewater treatment. The current work investigates the photocatalytic reduction of cadmium and selenium species as the presence of these elements in water are of environmental concern. Although TiO2 has been widely used for the photocatalytic process, its light absorption is limited to the UV region of the solar spectrum. Hence, the current project also explores the possibility to deposit cadmium selenide (CdSe) onto TiO2 to extend the photoresponse to the visible region. This study demonstrated that cadmium (Cd(II)) could be reduced to its metallic form by photocatalysis. The choice of hole scavengers and reaction pH are of importance in determining whether the photocatalytic reduction reaction will occur. It is also essential that both Cd(II) and organic additives are adsorbed on the surface of TiO2. A mechanism for cadmium photoreduction in the presence of formate as the hole scavenger was proposed. The current investigation elucidated the mechanism for the photoreduction of selenite (Se(IV)). Selenite was found to be photoreduced to its elemental form (Se(0)) as films, by direct photoreduction of Se(IV), and as discrete particles, by the reaction between Se(IV) and selenide (Se(2-)) ions. The Se(2-) ions are believed to have been generated from the 6 electron photoreduction of Se(IV) and/or the further photoreduction of the Se(0) deposits. Photocatalytic reduction reactions of Se(IV) and selenate (Se(VI)) using different commercial TiO2 materials was also studied. The current work also successfully deposited CdSe by photocatalysis using Se-TiO2 obtained from the photoreduction of Se(IV) and Se(VI). The mechanism for CdSe deposition was clarified and attributed to the reaction of Cd(II) present in the system and the Se(2-) released from the reduction of Se(0) upon further illumination. The Se??TiO2 photocatalysts obtained from the photoreduction of different selenium precursors (Se(IV) and Se(VI)) resulted in the dominance of different morphologies of the CdSe particles. This suggests a new approach to manipulate the properties of CdSe during its formation, and hence control over electrical and optical properties of this semiconductor.

Nonradiative decay of excitons is a competing process to Multi-Exciton Generation (MEG) in nanoparticles. Nonradiative decay of single excitons with sufficient energy to generate bi-excitons in Cd₂₀ Se₁₉ and Cd₈₃ Se₈₁ nanoparticles was studied using Tully's Molecular Dynamics with Quantum Transitions (MDQT) method and a CdSe pseudopo- tential. Exciton decay rates increase with increases in nanoparticle temperature and density of lower-lying excitonic states. There did not appear a significant effect of size on energy decay rates. The decay dynamics generally follow a gradual decay with transitions between nearby states. This is punctuated by periodic, short-lived periods of rapid downhill tran- sitions that result in a large proportion of excess exciton energy being transferred to the vibrational motion of the nanoparticle. The time for relaxation to below the 2.0E[subscript g] cutoff was on the order of 1ps. / text

Cadmium sulfide and cadmium selenide are important materials for applications such as photoconductive cells, photovoltaic cells and other electrooptical devices. Generally, these devices use single crystals. However, reasonable efficiencies have been observed by using polycrystalline films on conducting substrates, which are easier to make and provide considerable savings on materials and energy. Polycrystalline CdS/CdSe films have been made by sputtering and solution spraying, compound evaporation, chemical vapor deposition, and many others. A recent technique involves the electrochemical deposition of CdS and CdSe from nonaqueous solvents. Preparation of these films is based upon the cathodic deposition from a nonaqueous solution of a cadmium salt and elemental sulfur and/or selenium. Although the technique is simple, no mechanistic information is known to optimize the conditions in which films of controlled stoichiometry, doping and crystallinity are made. This research has the purpose to understand the mechanism of the formation of polycrystalline films of CdS and CdSe by electrochemical deposition in dimethylsulfoxide. This approach to the problem makes use of electrochemical techniques such as rotating ring disc electrode, linear scan voltammetry, high pressure liquid chromatography coupled with ultraviolet and electrochemical detection. By the rotating ring disc electrode technique, we have studied the kinetic parameters for the reduction of sulfur, selenium, cadmium, and the electroChemical formation of CdS and CdSe for temperatures from 25 - lOO°C. The results show that rates of initie.l electron transfer for the reduction of these species are moderately rapid, and secondly, that the reverse reaction is irreversible and involves additional steps. Studies of solubility of selenium with temperature reveal that its solubility is enhanced by the addition of sulfur. Understanding the electrochemical behavior of sulfur-selenium mixtures is of great importance to produce mixed semiconductive films with more adequate bandgaps for use with solar spectrum. Electrochemistry of sulfur-selenium mixtures are no different from that of sulfur alone. High pressure liquid chromatography separations with spectroscopic and electrochemical detectors have shown that sulfur solutions contain 86 and 87 fractions which are not electrochemically active.

No description available.

Ho, Yee Man Martina = 硒化鎘三維納米結構之製作及其感應脫氧核糖核酸之應用潛能 / 何綺雯. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / Abstract also in Chinese. / Ho, Yee Man Martina = Xi hua ge san wei na mi jie gou zhi zhi zuo ji qi gan ying tuo yang he tang he suan zhi ying yong qian neng / He Qiwen. / Chapter Chapter 1 --- Introduction / Chapter 1 --- Photovoltaic properties of CdSe --- p.1 / Chapter 1.1 --- Quantum size effect --- p.1 / Chapter 1.2 --- Synthesis of CdSe nanostructures --- p.3 / Chapter 1.3 --- Electrochemical sensing of CdSe nanostructures --- p.4 / Chapter 1.3.1 --- Surface passivation and functionalization of CdSe nanostructures --- p.5 / Chapter 1.4 --- Electronic properties of nanocrystalline semiconductor electrode --- p.6 / Chapter 1.4.1 --- Band alignment --- p.6 / Chapter 1.4.2 --- Interfacial charge transfer process --- p.9 / Chapter 1.4.3 --- Surface traps and adsorbed molecules --- p.10 / Chapter 1.4.4 --- DNA molecules as a capping group --- p.11 / Chapter 1.5 --- Literatures review in DNA sensing --- p.12 / Chapter 1.6 --- Present study --- p.14 / Chapter 1.6.1 --- Objective --- p.14 / Chapter 1.6.2 --- General methodology --- p.15 / Chapter Chapter 2 --- Experimental / Chapter 2.1 --- Introduction into the instrumentation of this project --- p.21 / Chapter 2.2 --- CHI Electrochemical workstation --- p.22 / Chapter 2.2.1 --- Linear sweep voltammetry --- p.24 / Chapter 2.2.2 --- Cyclic voltammetry --- p.24 / Chapter 2.2.3 --- Multiple potential step --- p.25 / Chapter 2.3 --- CEM Microwave-assisted chemical synthesizer --- p.27 / Chapter 3.1 --- Morphological examination by scanning electron microscopy --- p.28 / Chapter 3.2 --- Elemental analysis by energy dispersive x-ray spectroscopy --- p.30 / Chapter 3.3 --- Crystal structure analysis by x-ray diffraction --- p.31 / Chapter 3.4 --- Surface compositional analysis by x-ray photoelectron spectroscopy --- p.32 / Chapter 3.5 --- Transmission electron microscopy --- p.34 / Chapter Chapter 3 --- Synthesis of 3D nanostructured CdSe multipod electrodes / Chapter 3.1 --- Introduction into the synthesis of CdSe MP electrode --- p.35 / Chapter 3.2 --- Recipe for the synthesis of CdSe NPs --- p.36 / Chapter 3.3 --- The synthesis of CdSe MPs --- p.37 / Chapter 3.3.1 --- Tuning the experimental parameters: Reaction temperature --- p.37 / Chapter 3.3.2 --- Tuning the experimental parameters: Reaction hold time --- p.46 / Chapter 3.3.3 --- Tuning in experimental parameters: Precursor molar ratio --- p.50 / Chapter 3.4 --- The fabrication of MP CdSe on a conductive substrate --- p.54 / Chapter 3.4.1 --- The electrodeposition of CdSe thin films on ITO/glass substrates --- p.55 / Chapter 3.4.2 --- The growth of CdSe MPs on CdSe/ ITO/glass --- p.57 / Chapter 3.5 --- The characterization of MP CdSe electrode --- p.57 / Chapter Chapter 4 --- Electrical and opto-electric characteristics of CdSe MP electrodes and their applications as platforms for the DNA recognition / Chapter 4.1 --- Introduction to the property characterization of CdSe MP electrodes --- p.62 / Chapter 4.2 --- DNA surface attachment --- p.64 / Chapter 4.2.1 --- Mechanism of DNA surface anchoring --- p.65 / Chapter 4.3 --- I-V characterization in PBS --- p.69 / Chapter 4.3.1 --- Experimental procedures of the I-V tests in PBS --- p.70 / Chapter 4.3.2 --- Results and discussions of I-V tests in PBS --- p.72 / Chapter 4.3.2.1 --- Exercising as-prepared CdSe MP electrode --- p.74 / Chapter 4.3.2.2 --- I-V characteristics of CdSe MP electrodes before and after ssDNA attachment --- p.75 / Chapter 4.3.2.3 --- I-V characteristics of CdSe MP electrodes before and after the dsDNA attachment --- p.76 / Chapter 4.3.2.4 --- "Photo-response of bare CdSe MP, ssDNA/CdSe MP and dsDNA/CdSe electrodes" --- p.77 / Chapter 4.4 --- "Photovoltaic I-V measurement in I3""/I"" redox electrolyte" --- p.79 / Chapter 4.4.1 --- Experimental procedures --- p.79 / Chapter 4.4.2 --- Results and discussions --- p.80 / Chapter 4.5 --- Possible application implied by the results --- p.88 / Chapter 4.5.1 --- DNA base pair mismatch identification --- p.91 / Chapter 4.5.2 --- Field-assisted DNA hybridization acceleration process --- p.92 / Chapter Chapter 5 --- Conclusions / Chapter 5.1 --- Conclusions --- p.95

This thesis investigates the biodistribution and toxicological effects of amphiphilic polymer coated CdSe/ZnS quantum dots (QDs) in two aquatic species, Daphnia magna (daphnia) and Danio rerio (zebrafish). The use of QDs in the life sciences has become common practice over the past decade. In addition QDs are being incorporated in commercially available light emitting diodes and photovoltaic solar cells. As the widespread commercial use of QDs increases, environmental release is inevitable, and water will contain the highest environmental concentrations based on life cycle assessments. Despite increased attention to the aquatic toxicology of nanomaterials in recent years, little information exists on the biological fate of QDs in aquatic organisms. Quantitative data on the uptake and excretion of QDs from daphnia and zebrafish were collected using fluorescence imaging paired with metal analysis. First, daphnia were examined after aqueous and dietary exposure to amphiphilic polymer coated CdSe/ZnS QDs. Surface coating influenced QD acute toxicity and high particle aggregation correlated with daphnia mortality. QDs were readily ingested by daphnia and accumulated in the intestines. High body burdens of 150-200 μg/g were found in the daphnia, with intestinal QD concentrations significantly elevated above the exposure media concentration. The slow elimination observed in daphnia suggested that trophic transfer of QDs to higher organisms may occur. Using daphnia and zebrafish as a model food chain revealed that QDs can transfer to zebrafish through dietary exposure with body burdens of 8-9.5 μg/g found. However, no biomagnification between daphnia and zebrafish was observed and the biomagnification factor (BMF = 0.04) was significantly less than one. This work demonstrates that aqueous and dietary exposures to QDs can result in high total body concentrations in aquatic organisms with little to no gross toxicity. The low acute toxicity observed for some surface coated QDs encourages further design optimization to improve the biocompatibility and reduce the environmental impact of QDs.

Luminescent quantum dots (QDs) or rods are semiconductor nano-particles that may be used for a wide array of applications such as in electro-optical devices, spectral bar coding, tagging and light filtering. In the case under investigation, the nano-particles are cadmium-selenide (CdSe), though they can be made from cadmium-sulfide, cadmium-telluride or a number of other II-VI and III-V material combinations. The CdSe quantum dots emit visible light at a repeatable wavelength when excited by an ultraviolet source. The synthesis of colloidal quantum dot nanoparticles is usually an organo-metallic precursor, high temperature, solvent based, airless chemical procedure that begins with the raw materials CdO, a high boiling point ligand, and a Se-trioctylphosphine conjugate. This investigation explores the means to produce quantum dots by this method and to activate the surface or modify the reaction chemistry with such molecules as trioctylphosphine oxide, stearic acid, dodecylamine, phenyl sulfone, aminophenyl sulfone, 4,4'dichlorodiphenyl sulfone, 4,4'difluorodiphenyl sulfone, sulfanilamide and zinc sulfide during the production to allow for further applications of quantum dots involving new chemistries of the outer surface. Overall, the project has been an interesting and successful one, producing a piece of equipment, a lot of ideas, and many dots with varied capping structures that have been purified, characterized, and stored in such a way that they are ready for immediate use in future projects. / Master of Science