Faraday Rotation Spectroscopy of Quantum-Dot Quantum Wells

Time-resolved Faraday rotation studies of CdS/CdSe/CdS quantum-dot quantum wells have recently shown that the Faraday rotation angle exhibits several well-defined resonances as a function of probe energy close to the absorption edge. Here, we calculate the Faraday rotation angle from the eigenstates of the quantum-dot quantum well obtained with k.p theory. We show that the large number of narrow resonances with comparable spectral weight observed in experiment is not reproduced by the level scheme of a quantum-dot quantum well with perfect spherical symmetry. A simple model for broken spherical symmetry yields results in better qualitative agreement with experiment.Comment: 9 pages, 4 figure

A Study of Carbon Formation and Prevention in Hydrocarbon-Fueled SOFC

The formation and removal of the carbonaceous deposits formed by n-butane and liquid hydrocarbons, such as n-decane and proprietary light and heavy naphthas, between 973 and 1073 K on YSZ and ceria-YSZ, has been studied to determine conditions for stable operation of direct-utilization SOFC. First, it is shown that deactivation of SOFC with Cu-ceria-YSZ anodes operating on undiluted n-decane, a mixture of 80% n-decane and 20% toluene, or light naphtha at temperatures above 973 K is due to filling of the pores with polyaromatic compounds formed by gas-phase, free-radical reactions. Formation of these compounds occurs at a negligible rate below 973 K but increases rapidly above this temperature. The rate of formation also depends on the residence time of the fuel in the anode compartment. Because steam does not participate in the gas-phase reactions, carbonaceous deposits could form even at a H2O:C ratio of 1.5, a value greater than the stability threshold predicted by thermodynamic calculations. Temperature-programmed-oxidation (TPO) measurements with 20% H2O in He demonstrated that carbon deposits formed in pure YSZ were unreactive below 1073 K, while deposits formed on ceria-YSZ could be removed at temperatures as low as 923 K. Based on these results, we discuss strategies for avoiding carbon formation during the operation of direct-utilization anodes on oil-based liquid fuels

Synthesis of CdS and CdSe nanocrystallites using a novel single-molecule precursors approach

The synthesis of CdS and CdSe nanocrystallites using the thermolysis of several dithioor diselenocarbamato complexes of cadmium in trioctylphosphine oxide (TOPO) is reported. The nanodispersed materials obtained show quantum size effects in their optical spectra and exhibit near band-edge luminescence. The influence of experimental parameters on the properties of the nanocrystallites is discussed. HRTEM images of these materials show well-defined, crystalline nanosized particles. Standard size fractionation procedures can be performed in order to narrow the size dispersion of the samples. The TOPO-capped CdS and CdSe nanocrystallites and simple organic bridging ligands, such as 2,2¢-bipyrimidine, are used as the starting materials for the preparation of novel nanocomposites. The optical properties shown by these new nanocomposites are compared with those of the starting nanodispersed materials

Photothermal Absorption Spectroscopy of Individual Semiconductor Nanocrystals

Photothermal heterodyne detection is used to record the first room-temperature absorption spectra of single CdSe/ZnS semiconductor nanocrystals. These spectra are recorded in the high cw excitation regime, and the observed bands are assigned to transitions involving biexciton and trion states. Comparison with the single nanocrystals photoluminescence spectra leads to the measurement of spectral Stokes shifts free from ensemble averaging

Electronic structure and optical properties of ZnS/CdS nanoheterostructures

The electronic and optical properties of spherical nanoheterostructures are studied within the semi-empirical $sp^{3}s^{*}$ tight-binding model including the spin-orbit interaction. We use a symmetry-based approach previously applied to CdSe and CdTe quantum dots. The complete one-particle spectrum is obtained by using group-theoretical methods. The excitonic eigenstates are then deduced in the configuration-interaction approach by fully taking into account the Coulomb direct and exchange interactions. Here we focus on ZnS/CdS, ZnS/CdS/ZnS and CdS/ZnS nanocrystals with particular emphasis on recently reported experimental data. The degree of carrier localization in the CdS well layer is analyzed as a function of its thickness. We compute the excitonic fine structure, i.e., the relative intensities of low-energy optical transitions. The calculated values of the absorption gap show a good agreement with the experimental ones. Enhanced resonant photoluminescence Stokes shifts are predicted.Comment: 6 pages, 4 Figures, revtex

Metastability in pressure-induced structural transformations of CdSe/ZnS core/shell nanocrystals

The kinetics and thermodynamics of structural transformations under pressure depend strongly on particle size due to the influence of surface free energy. By suitable design of surface structure, composition, and passivation it is possible, in principle, to prepare nanocrystals in structures inaccessible to bulk materials. However, few realizations of such extreme size-dependent behavior exist. Here we show with molecular dynamics computer simulation that in a model of CdSe/ZnS core/shell nanocrystals the core high pressure structure can be made metastable under ambient conditions by tuning the thickness of the shell. In nanocrystals with thick shells, we furthermore observe a wurtzite to NiAs transformation, which does not occur in the pure bulk materials. These phenomena are linked to a fundamental change in the atomistic transformation mechanism from heterogenous nucleation at the surface to homogenous nucleation in the crystal core. Our results suggest a new route towards expanding the range of available nanoscale materials

Type-II Colloidal Quantum Wells: CdSe/CdTe Core/Crown Heteronanoplatelets

Solution-processed quantum wells, also known as colloidal nanoplatelets (NPLs), are emerging as promising materials for colloidal optoelectronics. In this work, we report the synthesis and characterization of CdSe/CdTe core/crown NPLs exhibiting a Type-II electronic structure and Type-II specific optical properties. Here, based on a core-seeded approach, the CdSe/CdTe core/crown NPLs were synthesized with well-controlled CdTe crown coatings. Uniform and epitaxial growth of CdTe crown region was verified by using structural characterization techniques including transmission electron microscopy (TEM) with quantitative EDX analysis and X-ray diffraction (XRD). Also the optical properties were systematically studied in these Type-II NPLs that reveal strongly red-shifted photoluminescence (up to similar to 150 nm) along with 2 orders of magnitude longer fluorescence lifetimes (up to 190 ns) compared to the Type-I NPLs owing to spatially indirect excitons at the Type-II interface between the CdSe core and the CdTe crown regions. Photoluminescence excitation spectroscopy confirms that this strongly red-shifted emission actually arises from the CdSe/CdTe NPLs. In addition, temperature-dependent time-resolved fluorescence spectroscopy was performed to reveal the temperature-dependent fluorescence decay kinetics of the Type-II NPLs exhibiting interesting behavior. Also, water-soluble Type-II NPLs were achieved via ligand exchange of the CdSe/CdTe core/crown NPLs by using 3-mercaptopropionic acid (MPA), which allows for enhanced charge extraction efficiency owing to their shorter chain length and enables high quality film formation by layer-by-layer (LBL) assembly. With all of these appealing properties, the CdSe/CdTe core/crown heterostructures having Type-II electronic structure presented here are highly promising for light-harvesting applications

Polarised Photoluminescence from Surface-Passivated PbS Nanocrystals

Effective surface-passivation of PbS nanocrystals in aqueous colloidal solution has been achieved following treatment with CdS precursors. The resultant photoluminescent emission displays two distinct components, one originating from the absorption band-edge and the other from above the absorption band-edge. We show that both of these components are strongly polarised but display distinctly different behaviours. The polarisation arising from the band-edge shows little dependence on the excitation energy while the polarisation of the above-band-edge component is strongly dependent on the excitation energy. In addition, time resolved polarisation spectroscopy reveals that the above-band-edge polarisation is restricted to the first couple of nanoseconds, while the band-edge polarisation is nearly constant over hundreds of nanoseconds. We recognise an incompatibility between the two different polarisation behaviours, which enables us to identify two distinct types of surface-passivated PbS nanocrystal.Comment: Preprint, 19 pages, 4 figure

Working with Commercially Available Quantum Dots for Immunofluorescence on Tissue Sections

Quantum dots are semiconductor fluorescent nanocrystals that exhibit excellent characteristics compared with more commonly used organic fluorescent dyes. For many years quantum dot conjugated products have been available in multiple forms for fluorescence imaging of tissue sections under the trademark name Qdot®. They have much increased brightness, narrow emission spectrum, large Stokes shift and photostability compared with conventional organic fluorescent dyes, which together make them the fluorophores of choice for demanding requirements. Vivid Qdots are recent replacements for original Qdots, modified to improve brightness, however this has affected the fluorescence stability in commonly used conditions for immunohistochemistry. We present here our investigation of the stability of original and Vivid Qdots in solution and in immunohistochemistry, highlight the potential pitfalls and propose a protocol for stable and reliable multiplex staining with current commercially available original and Vivid Qdots