Nanostructured composites are attracting intense interest for electronic and optoelectronic device applications, specifically as active elements in thin film photovoltaic (PV) device architectures. These systems implement fundamentally different concepts of enhancing energy conversion efficiencies compared to those seen in current commercial devices. This is possible through considerable flexibility in the manipulation of device-relevant properties through control of the interplay between the nanostructure and the optoelectronic response. In the present work, inorganic nanocomposites of semiconductor Ge embedded in transparent conductive indium tin oxide (ITO) as well as Ge in zinc oxide (ZnO) were produced by a single step RF-magnetron sputter deposition process.It is shown that, by controlling the design of the nanocomposites as well as heat treatment conditions, decreases in the physical dimensions of Ge nanophase size provided an effective tuning of the optical absorption and charge transport properties. This effect of changes in the optical properties of nanophase semiconductors with respect to size is known as the quantum confinement effect. Variation in the embedding matrix material between ITO and ZnO with corresponding characterization of optoelectronic properties exhibit notable differences in the presence and evolution of an interfacial oxide within these composites. Further studies of interfacial structures were performed using depth-profiling XPS and Raman spectroscopy, while study of the corresponding electronic effects were performed using room temperature and temperature-dependent Hall Effect. Optical absorption was noted to shift to higher onset energies upon heat treatment with a decrease in the observed Ge domain size, indicating quantum confinement effects within these systems. This contrasts to previous investigations that have involved the introduction of nanoscale Ge into insulating, amorphous oxides. Comparison of these different matrix chemistries highlights the overarching role of interfacial structures on quantum-size characteristics. The opportunity to tune the spectral response of these PV materials, via control of semiconductor phase assembly in the nanocomposite, directly impacts the potential for the use of these materials as sensitizing elements for enhanced solar cell conversion efficiency.

In 2012 the net world electricity generation was 21.56 trillion kilowatt hours. Photovoltaics only accounted for only 0.1 trillion kilowatt hours, less than 1 % of the total power. Recently there has been a push to convert more energy production to renewable sources. In recent years a great deal of interest has been shown for dye sensitized solar cells. These devices use inexpensive materials and have reported efficiencies approaching 12% in the lab. Here methods have been studied to improve upon these, and other, devices. Different approaches for the addition of gold nanoparticles to TiO2 films were studied. These additions acted as plasmonic and light scattering enhancements to reported dye sensitized devices. These nanoparticle enhancements generated a 10% efficiency in device performance for dye sensitized devices. Quantum dot (QD) sensitized solar cells were prepared by successive ionic layer adsorption and reaction (SILAR) synthesis of QDs in mesoporous films as well as the chemical attachment of colloidal quantum dots using 3-mercaptopropionic acid (3-MPA). Methods of synthesizing a copper sulfide (Cu2S) counter electrode were investigated to improve the device performance. By using a mesoporous film of indium tin oxide nanoparticles as a substrate for SILAR growth of Cu2S catalyst, an increase in device performance was seen over that of devices using platinum. These devices did suffer from construction drawbacks. This lead to the development of 3D nanostructures for use in Schottky photovoltaics. These high surface area devices were designed to overcome the recombination problems of thin film Schottky devices. The need to deposit a transparent top electrode limited the success of these devices, but did lead to the development of highly ordered metal nanotube arrays. To further explore these nanostructures depleted heterojunction devices were produced. Along with these devices a new approach to depositing lead sulfide quantum dots was developed. This electrophoretic deposition technique uses an applied electric field to deposit nanoparticles onto a substrate. This creates the possibility for a low waste method for depositing nanocrystals onto nanostructured substrates.

Luminescent semiconductor quantum dots (QDs) are extensively researched for use in biological applications. They have unique optical and physical properties that make them excellent candidates to replace conventional organic dyes for cellular labeling, multiplexing, nucleic acid detection, and as generalized probes. The primary focus of this dissertation was to utilize quantum dots for improvement in immunoassays. Specifically, atherosclerosis biomarkers were detected simultaneously in an effort to demonstrate advances in early detection diagnostics. Quantum dot-antibody bioconjugates were prepared by encapsulation into mesoporous silica and functionalized with thiol and amine groups to enable bioconjugation. Functionalization of the mesoporous silica quantum dot composites facilitated biocompatibility for use with biological buffers in immunoassays. These bioconjugates were used in a sandwich immunoassay to detect atherosclerosis biomarkers IL-15 and MCP-1. Sandwich assays employ capture antibodies immobilized onto a well plate to bind as much of the antigen as possible. The capture antibodies increased binding by at least 4 times the amount of antigen bound to the surface of a direct detection assay. The sandwich immunoassay was able to detect 1 pg/mL of IL-15 and 50 pg/mL of MCP-1 biomarkers. Human serum albumin nanoparticles (HSAPs) were synthesized via a desolvation and crosslinking method. Human serum albumin is a versatile protein being used in a variety of applications. Quantum dots were loaded into HSAPs as potential detection probes for immunoassays. Efficient loading was not achieved, and the assay was unable to improve current detection limits. Controlled release studies were explored using HSAPs loaded with superparamagnetic iron oxide nanoparticles and a fluorescent drug analog. Exposure to a magnetic field resulted in degradation of the HSAPs. The fluorophore was released and measured to examine how cancer drugs might be controlled through a magnetic field. Gold nanorods and an anticancer drug, Sorafenib, were also encapsulated into HSAPs for treatment of renal cell carcinoma in vivo. Laser irradiation treatment combined with Sorafenib resulted in 100% tumor necrosis and total elimination of any viable tumor present. HSAPs have demonstrated remarkable potential as drug delivery nanocarriers.

Nanometer-sized semiconductor crystals, termed ‘quantum dots’, are of fundamental interest because of their size-tunable properties. Three-dimensional quantum confinement of charge carriers by the small crystal size results in discrete atomic-like electronic states. This dissertation describes the synthesis and in-depth characterization of lead chalcogenide colloidal quantum dots for forthcoming applications as near-infrared single photon emitters. An efficient single photon source that operates at telecommunication wavelengths (between 1.3 and 1.6 µm) is a basic requirement for many photonic quantum technologies, such as quantum computing and quantum cryptography. Chapters 1 and 2 of this work provide an introduction to colloidal quantum dots and their use as single photon emitters. It includes a description of photonic crystal microcavities and their ability to enhance the spontaneous emission rate of quantum dots. The synthesis and basic characterization of PbSe and PbS quantum dots is then discussed in chapter 3. In particular, a new synthetic method for the preparation of highly photoluminescent PbS quantum dots is presented. PbSe/CdSe core/shell quantum dots prepared by a cation exchange reaction are also described and a significant improvement in photo-stability is shown. Chapter 3 concludes with a description of three different surface modification techniques. PbSe core and PbSe/CdSe core/shell materials are investigated further in chapter 4 by advanced characterization techniques that include high-angle annular dark field (HAADF) imaging, energy-filtered transmission electron microscopy (EF-TEM) imaging, energy-dependent X-ray photo-electron spectroscopy (XPS), small angle X-ray scattering (SAXS), and small angle neutron scattering (SANS). The information obtained from these techniques is combined to form a structural model of the PbSe core and PbSe/CdSe core/shell quantum dots with greater complexity than previously reported. In chapter 5, the temperature-dependent photoluminescence from PbSe and PbSe/CdSe core/shell quantum dots is discussed and a thermal model is presented that accounts for the large (non-trivial) temperature dependence of the Stokes shift and photoluminescence lineshape over the entire temperature range (4.5 to 295 K). Chapter 6 examines two scalable methods to integrate the colloidal quantum dots into silicon two-dimensional photonic crystal slab microcavities (a requirement for efficient single photon emission). Finally, conclusions and possible future work are discussed in chapter 7. / Graduate

In this thesis, luminescent lanthanide-doped nanocrystals, and lead-based quantum dots nanocrystals are explored as alternative bioimaging agents to fluorescent proteins and organic fluorophores for deep-tissue imaging. The first chapter gives a brief introduction on the aforementioned nanocrystals and their special optical properties. In chapter 2 the simple changes in the drying and baking temperature of the Yb3+ and Ho3+ doped LaF3 nanocrystals-silica sol-gel mixture aid in the explanation of the formation of two types of silica. The difference in the phonon energies of the two types of silica is found to control effectively the ratio of red to green emissions obtained from the upconversion process. However, the nanocrystals do not disperse in water making them unsuitable for bioimaging. Chapter 3 describe the synthesis of NaYF4 nanocrystals doped with Yb3+/Er3+ or Yb3+/Tm3+ ions followed by two surface modification strategies (intercalation and crosslinking) to disperse them in physiological buffers and biological growth media. Of the two methods, the crosslinked polymer coating of the nanocrystals alone exhibits stability in aforementioned media. In chapter 4 the applicability of lanthanide-doped NaYF4 nanocrystals are studied as bioimaging agents in two-photon upconversion laser scanning microscopy for deep-tissue imaging. Their performance as bioimaging agents was not better than fluorescent proteins and organic molecules. On the other hand with two-photon upconversion wide field microscopy (TPUWFM), brain blood vessels over a depth of 100 µm could well be separated. Furthermore, with the 800 nm emission from Tm3+ ions one can image twice as deep as the green emission with TPUWFM. In chapter 5, probing the NaYF4 nanocrystals with energy-dependent XPS shows that, the Y3+ ions on the surface of the nanocrystals are different from the ones present inside the nanocrystals. This chapter is concluded with a preliminary investigation of Yb3+ and Tm3+ doped NaYF4 with resonant XPS. Chapter 6 examines four different types of surface modification strategies to transfer hydrophobic lead-based quantum dots to physiological buffers and biological growth media. Of the four methods, the crosslinked polymer coating of quantum dots alone exhibits colloidal stability and the QDs retain their luminescence in aforementioned media over several months. The conclusions and future outlook for the work are elucidated in chapter 7. / Graduate

Atomic clusters are attractive candidates for building motifs for new nano-assembled materials with desirable properties. At this nano-regime of matter, the size, shape, and composition of clusters changes their electronic structure and hence their properties. Computational modeling must work hand in hand with experiment to provide robust descriptions of the geometries and energetics of atomic clusters and how they might behave in a nano-assembled material. To this end, we have investigated three distinct species as model systems: antimony oxides SbxOy (x = 1, 2; y = 0 - 3), metal ion-solvent complexes Mm(NH3)n (M = Bi, Pb; m = 1 - 2, n = 0 - 4), and quantum dots Z10H16 (Z = Si, Ge) and β-Sn12H24. Their geometries and electronic structures have been determined using gradient-corrected density functional theory. The relative stabilities for antimony oxides have been examined by the respective comparison of highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps and atomization energies. The superior electronic stability of Sb2O3 is indicated by its closed shell structure, wide HOMO-LUMO gap calculated to be 3.11 eV, and high atomization energy of 4.21 eV. Spin-orbit corrections were necessary for accurate calculation of the metal-solvent energetics, closing the gap between experimental and theoretical values by 1.05 eV for the electron affinity of the Pb atom. Quantum dot modeling of the well-established Si and Ge as well as the less-investigated Sn illuminated the accuracy of the CEP basis sets and the B3LYP functional over other DFT computational routes for clusters containing elements beyond the third row. Throughout, the results correlate well with experiment and higher order ab initio methods where data is available. These comparisons validate the accuracy of the computational routes used. This document was prepared in the Linux Ubuntu Open Office Suite 2.4.1.

Semiconductor nanowires have attracted considerable attention as possible source for lasers and optical storage media. We report the fabrication and optical characterization of ZnO and CdS nanowires. The former are produced by electrochemical deposition of Zn inside nanoporous alumina films containing regimented arrays of 10nm, 25nm and 50 nm diameter pores, followed by room temperature chemical oxidization. Fluorescence spectroscopy shows different characteristics associated with different sample diameter. The 50 nm ZnO nanowires show an exciton recombination peak and an additional peak related to the deep trap levels. 25 nm ZnO nanowires show a only the exciton recombination peak, which is red shifted, possibly due to quantum confined Stark effect associated with built in charges in the alumina. This feature can be exploited to produce light emitting devices whose frequency can be modulated with an external electric field. Such devices could be novel ultra-violet frequency modulators for optical communication and solar blind materials. In addition, we have investigated fluorescence spectra of 10-, 25- and 50-nm diameter CdS nanowires (relative dielectric constant = 5.4) self assembled in a porous alumina matrix (relative dielectric constant = 8-10). The spectra reveal peaks associated with free electron-hole recombination. The 10-nm wire spectra show an additional lower energy peak due to exciton recombination. In spite of dielectric de-confinement caused by the insulator having a higher dielectric constant than the semiconductor, the exciton binding energy increases almost 8-fold from its bulk value in the 10 nm wires. This increase is most likely due to quantum confinement accruing from the fact that the exciton Bohr radius (~5 nm) is comparable to or larger than the wire radius, especially if side depletion is taken into account. Such an increase in the binding energy could be exploited to make efficient room temperature luminescent devices in the visible range.

Exciting periods of scientific research are often associated with discoveries of novel materials. Such period was brought about by the successful preparation of graphene which is a 2D allotrope of carbon with remarkable electronic, optical and mechanical properties. Functional graphene-based nanocomposites have great promise for applications in various fields such as energy conversion, opteoelectronics, solar cells, sensing, catalysis and biomedicine. Herein, microwave and laser-assisted synthetic approaches were developed for decorating graphene with various semiconductor, metallic or magnetic nanostructures of controlled size and shape. We developed a scalable microwave irradiation method for the synthesis of graphene decorated with CdSe nanocrystals of controlled size, shape and crystalline structure. The efficient quenching of photoluminescence from the CdSe nanocrystals by graphene has been explored. The results provide a new approach for exploring the size-tunable optical properties of CdSe nanocrystals supported on graphene which could have important implications for energy conversion applications. We also extended this approach to the synthesis of Au-ceria-graphene nanocomposites. The synthesis is facilely conducted at mild conditions using ethylenediamine as a solvent. Results reveal significant CO conversion percentages between 60-70% at ambient temperatures. Au nanostructures have received significant attention because of the feasibility to tune their optical properties by changing size or shape. The coupling of the photothermal effects of these Au nanostructures of controlled size and shape with GO nanosheets dispersed in water is demonstrated. Our results indicate that the enhanced photothermal energy conversion of the Au-GO suspensions could to lead to a remarkable increase in the heating efficiency of the laser-induced melting and size reduction of Au nanostructures. The Au-graphene nanocomposites are potential materials for photothermolysis, thermochemical and thermomechanical applications. We developed a facile method for decorating graphene with magnetite nanocrystals of various shapes (namely, spheres, cubes and prisms) by the microwave-assisted-reduction of iron acetylacetonate in benzyl ether. The shape control was achieved by tuning the mole ratio between the oleic acid and the oleyamine. The structural, morphological and physical properties of graphene-based nanocomposites described herein were studied using standard characterization tools such as TEM, SEM, UV-Vis and PL spectroscopy, powder X-ray diffraction, XPS and Raman spectroscopy.

Ce travail porte sur la croissance épitaxiale et la caractérisation optique de boîtes quantiques d’InAs/InP(001) en faible densité en vue de la réalisation de nouveaux composants nanophotoniques émettant à 1,55 µm. Les propriétés structurales et optiques des îlots ont été corrélés pour différents paramètres de croissance d’un système d’épitaxie par jet moléculaire à sources solides. Nos résultats soulignent l’influence des reconstructions de surface d’InAs sur la forme des îlots. Des boîtes, plutôt que des bâtonnets allongés généralement observés,peuvent être directement formées dans des conditions de croissance adéquates. Une transition de forme de bâtonnets vers des boîtes est également démontrée par des traitements postcroissance sous arsenic. Les faibles densités de boîtes sont obtenues pour des faibles épaisseurs d’InAs déposées. Leur émission est facilement contrôlée à 1,55 µm par une procédure d’encapsulation spécifique appelé « double cap ». Quelques propriétés des boîtes individuelles d’InAs/InP sont ensuite évaluées. Les études de micro-photoluminescence révèlent des pics d’émission très fins et distincts autour de 1,55 µm confirmant les propriétés« quasi-atomiques » de ces boîtes uniques. Enfin, nous proposons pour la première fois une méthode à haute résolution spatiale qui permet d’étudier le transport de charges autour d’une boîte unique grâce à une technique de cathodoluminescence à basse tension d’accélération.Une mesure directe de la longueur de diffusion des porteurs avant capture dans une boîte a été obtenue. Ces résultats ouvrent de nouvelles perspectives quant à l’intégration de ces boîtes uniques dans des microcavités optiques pour la réalisation de sources de lumières quantiques à 1,55 µm. / This thesis focus on the epitaxial growth and optical characterization of diluted InAs/InP(001) quantum dots for the realisation of new nanophotonic devices emitting at 1.55μm. The structural and optical properties of the quantum islands are correlated to different growth parameters of a solid source molecular beam epitaxy system. Our results highlight the influence of InAs surface reconstructions on the island shape. Dots rather than elongated dashes usually observed can be directly formed by adequate growth conditions. Dash to dot shape transition is also demonstrated by post-growth treatments. Low dot densities are obtained for small InAs deposited thickness. Their emission wavelength is easily tuned to1.55 µm using the “double cap” procedure for the growth of the InP capping layer. Optical properties of such single InAs/InP quantum dots are then evaluated. Microphotoluminescence studies reveal sharp and well separated emission lines near 1.55 µm from single dots confirming their atom-like properties. Last, we propose for the first time a highspatial resolution method to study the carrier transport in the vicinity of a single quantum dotusing a low-voltage cathodoluminescence technique. A direct measurement of the carrier diffusion length before capture into one dot has been obtained. These results open the way to the integration of these single dots into optical micro-cavities for the realisation of quantumlight sources at 1.55 µm.

Luminescent quantum dots have attracted great interest in recent years among biological researchers since they provide solutions to problems associated with use of organic fluorophores in cellular studies. Quantum dots show high photostability, high emission quantum yield, narrow and symmetric emission peaks and size-dependent wavelength tunability. The objective of my PhD studies was to develop CdSe/ZnS quantum dot-based probes and utilize them in cellular assays. The first phase of the work was to develop luminescent quantum dot fluorescence resonance energy transfer (FRET) based probes for protease activity. The probes were based on FRET interactions between quantum dots that serve as donors and rhodamine molecular acceptors that were immobilized to the surface of the quantum dots through peptide linkers, which contained selective enzymatic cleavage sites. Upon enzymatic cleavage of the peptide linkers, the rhodamine molecules no longer provided an efficient energy transfer channel to the quantum dots, which brightened the previously quenched quantum dots. The probes were applied to detect enzyme activity, screen enzyme inhibitors, and discriminate between normal and cancerous cells primarily because of the difference in the proteolytic activity in extracellular matrices. The second phase of my work was to take advantage of FRET and quantum dots to develop pH sensor. First quantum dots were modified with metallothionein (MT) to be water-soluble and biocompatible. The MT-coated quantum dots were labeled with Rhodamine through the formation of amide bonds with å-amine group of lysine in MT peptide to form the probes. FRET efficiency between quantum dots (donor) and rhodamine (acceptor) was pH dependent. The final phase of my studies focused on the first preparation of reversible quantum dot-based cellular probes for labile iron. The MT coated quantum dots was modified with EDTA to form probes. When captured by the EDTA molecules, iron ions quenched the emission of quantum dots. Removal of iron from the quantum dot surface by free EDTA or other iron chelators with higher binding affinity resulted in a rise in the luminescence of quantum dots. The analytical properties of the probes including sensitivity, selectivity, and reversibility were characterized. Intracellular assays in iron-enriched astrocytes will be carried out.