In this thesis, cadmium selenide (CdSe) quantum dots (QDs) are synthesized and characterized for patterning applications as well as for photovoltaic devices. The QDs were patterned and embedded into various polymers to form fluorescent composites. Their photophysical properties were investigated in detail. Through template assisted deposition the QDs-polymer composites were patterned into fluorescent nanorods. CdSe QDs were combined with multi-wall carbon nanotubes (CNTs) using a synthesized organic perylene derivative dye (N,N'-di(ethanethiol)-perylene-3,4,9,10-tetracarboxyl diimide) (ETPTCDI) as a link between QDs and CNTs. Upon testing, the QDs-ETPTCDI-CNTs nanocomposite displayed photoactive properties. Photophysical quenching studies of QD-ETPTCDI-CNTs provided better understanding of the electron-hole transfer of each component in the nanocomposite. The nanocomposite material was patterned onto microelectrode devices for photocurrent measurements under an AM1.5 solar simulated light source. These nanocomposites can be used as photovoltaic devices. The preliminary characterization studies of the device show excellent photoresponse under AM1.5 solar simulated light. The band gap alignment of each component of the nanocomposite and the charge transfer kinetics are the key to efficient electron-hole transfer. Optimization of the semiconducting material's interface can potentially make these nanocomposites a system for photovoltaic-based devices.

This dissertation focused on the applications of self-assembled monolayers (SAMs) technique for the investigation of molecule based electronics, plasmon coupling between CdSe quantum dots and metal nanoparticles (MNPs), and copper ion detection using enhanced emission of CdSe quantum dots (QDs). The SAMs technique provides an approach to establish a robust, two-dimensional and densely packed structure which can be formed on metal or semiconductor surfaces. This allows for the design of molecular assemblies that can be used to understand the details of molecular conduction by employing various electrical testbeds. In this work, the strategy of molecular assemblies was used to pattern metal nanoparticles on GaAs surfaces, thereby furnishing a platform to explore the interactions between QDs and MNPs. The enhanced emission of CdSe QDs by MNPs was then used as a probe for ultrasensitive, cheap, and rapid copper(II) detection. The study is divided into three main facets. The first one aimed at controlling electron transport behavior through porphyrins on surfaces with an eye toward optoelectronic and light harvesting applications. The binding of the porphyrin molecules to Au surfaces, pre-covered with a dodecanethiol matrix, was characterized by FTIR, XPS, AFM, STM, of. This study has shown that the perfluoro coupling group between the porphyrin macrocycle and the thiol tether may provide a means of controlling the tunneling behavior. The second area of this study focused on the design of a simple platform to examine the coupling between metal nanostructures and quantum dot assemblies. Here we demonstrate that by using a patterned array of Au or Ag nanoparticles on GaAs, plasmon enhanced photoluminescence (PL) can be directly measured and quantified by direct scaling of regions with and without metal nanostructures. The third field presented a simple manner for using the enhanced PL of CdSe QDs as a probe for ultrasensitive Cu2+ ion detection and quantitative analysis. The PL of QDs was enhanced by two processes: first, photobrightening of the material, and second, plasmonic enhancement by coupling with Ag nanoprisms. This strong PL leads to a high sensitivity of the QDs over a wide dynamic range for Cu2+ detection, as Cu2+ efficiently quenches the QD emission.

This thesis summarizes the methods of preparation and optical properties of hybrid assemblies of Au NPs and cadmium selenide (CdSe) QDs. First chap-ter deals with the literature survey and theoretical aspects of plasmonics and discussions on optical excitations of metal (plasmons) and semiconducting QDs (excitons). Variation of energy levels of CdSe QDs and its optical properties i e. absorption and emission properties under strong confinement regime have been discussed with respect to effective mass approximation (EMA) model. This is followed by the discussion on optical properties of Au NPs and rods, describing absorption properties, based on Mie theory. Size and shape depen-dent variation of absorption properties. Theoretical discussions of collective effects in QDs assemblies and plasmonic interactions with the QDs assemblies i.e. plasmonic Dicke effect and metal nanoantenna interaction with CdSe QDs arrays is provided. In the second chapter a discussion on experimental techniques used for the study is provided. It starts with a discussion on the synthesis methods for CdSe QDs and Au NPs/rods with different capping ligands. Different techniques of preparation of CdSe QDs assemblies and their hybrid with metallic nanoparti-cles has been discussed. Further discussion on optical microscopy techniques, confocal, near field scanning microscopy (NSOM), Brewster angle microscopy and electron microscopy techniques i. e transmission electron microscopy and scanning electron microscopy and thermogravimetry analysis of the samples is provided. In the third chapter the details of the different self-assembly methods of preparation of hybrid assemblies of CdSe QDs and Au NPs /rods are given. The different strategies are used for different type of hybrids. In first method of Langmuir-Blodgett (LB) , effect of different capping agents, core size, and number ratios of Au NPs/rods to CdSe QDs, effect of anisotropy of Au NPs on the LB films of CdSe QDs assemblies is discussed. In another method of dip coating several control parameters like dip time, concentration of the solution and dip speed of transferring an aligned GNRs is given. Finally a combination of LB and dip coating methods is described for transferring aligned GNRs over a compact layer of CdSe QDs. At the end, a section is devoted to hit and trials of self-assemblies of hybrid of GNRs and CdSe QDs using LB method, the failures of which resulted in devising a method which uses a combination of LB and dip coating. In fourth chapter effects of plasmons on the collective emission of CdSe QDs assemblies are investigated. A plasmonic tuning of photoluminescence from semiconducting QD assemblies using Au NP in different ratio and different packing density has been discussed. We have described how the emission from a closed pack assemblies, prepared with different packing densities depends on the packing density and extent of spectral overlap between QD photolumi-nescence and the metal nanoparticle absorbance. We have provided possible evidence for plasmon mediated coherent emission enhancement from some of these assemblies from the case of strong spectral overlap between CdSe QDs and Au nanoparticle. In fifth chapter, we have demonstrated non local far field enhancement of PL in QDs assemblies induced by isolated and partially aligned GNRs nano-antenna located on such assemblies. It is shown that the emission is also anisotropic with the maxima being near such GNRs assembly which decays to finite, nonzero and significantly large values even away from the vicinity of any such assemblies. For this novel effect it is shown to have a clear spec-tral dependence. It is shown to be maximum when the longitudinal surface plasmon resonance absorption maxima is resonant with the CdSe QD photolu-minescence maxima and the excitation wavelength and is always non-existent for the off resonant case. We have also shown that finite difference time do-main simulations could model some of the observed near field effects but the far field effects could not be modelled in such simulations.

This thesis reports a passive method for Fermi level regulation in quantum dot assemblies through ground state transfer between QDs. Here, ZnTe/CdS, and PbSe/CdSe core/shell QDs were used as valence band electron donors, while Cu containing CdS or ZnSe acts as electron acceptor QDs. Prior to study of ground state charge transfer process, this report discusses the synthesis of ZnTe/CdS, and PbSe/CdSe core shell QDs, which are later used to study charge transfer. Since ZnTe QDs are unstable and prone to oxidation, a CdS coated ZnTe QDs were used. Growing a CdS shell on ZnTe core is difficult because high reduction potential of Te. To overcome this problem, partially reduced sulphur is used for the synthesis of ZnTe/CdS. The peculiar optical properties exhibited by ZnTe/CdS also have been discussed. Even though the synthesis of Lead chalcogenide nanoparticles has been investigated previously, certain inconsistencies between the behavior expected from known mechanisms and empirical observations. An anion exchange mechanism is proposed and demonstrated to be involved in PbSe formation. Both ZnTe and PbSe based QDs are extensively used to study hole injection and copper containing QDs were used as acceptors. The charge transfer has been studied using optical spectroscopy. The structure and composition of the assemblies was identified using powder crystallography, electron-microscopy and composition analysis. The unique physical and chemical properties of these materials are exciting both fundamentally as well as from the point of view of applications.