Semiconductor nanocrystal quantum dots (NQDs) comprise an important class of inorganic fluorophores for applications from optoelectronics to biology. Unfortunately, to date, NQD optical properties (e.g., their efficient and particle-size-tunable photoluminescence) have been susceptible to instabilities at the bulk and single-particle levels. Specifically, ensemble quantum yields (QYs) in emission are dependent upon NQD surface chemistry and chemical environment, while at the single-particle level, NQDs are characterized by significant fluorescence intermittency (blinking) that hinders applications as single-photon light sources for quantum informatics and biolabels for real-time monitoring of single biomolecules. Furthermore, while NQDs are significantly more photostable than their organic dye counterparts, traditional NQDs photobleach over periods of seconds to many minutes. Here, we demonstrate for the first time that by encapsulating the NQD core in a sufficiently thick inorganic shell, we are able to divorce NQD function from NQD surface chemistry and chemical environment. We show that our "giant" NQDs (g-NQDs) are functionally distinct from standard core-only, core/shell and even core/multishell NQDs. g-NQDs are substantially less sensitive to changes in surface chemistry. They do not photobleach under continuous laser excitation over periods of several hours repeated over several days, and they exhibit markedly different blinking behavior; >20% of the g-NQDs do not blink, while >40% have on-time fractions of >80%. All of these observations are in stark contrast with control samples comprising core-only and standard, thinner core/multishell NQDs.

Magnetic doping of semiconductor nanostructures is actively pursued for applications in magnetic memory and spin-based electronics. Central to these efforts is a drive to control the interaction strength between carriers (electrons and holes) and the embedded magnetic atoms. In this respect, colloidal nanocrystal heterostructures provide great flexibility through growth-controlled 'engineering' of electron and hole wavefunctions in individual nanocrystals. Here, we demonstrate a widely tunable magnetic sp-d exchange interaction between electron-hole excitations (excitons) and paramagnetic manganese ions using 'inverted' core-shell nanocrystals composed of Mn(2+)-doped ZnSe cores overcoated with undoped shells of narrower-gap CdSe. Magnetic circular dichroism studies reveal giant Zeeman spin splittings of the band-edge exciton that, surprisingly, are tunable in both magnitude and sign. Effective exciton g-factors are controllably tuned from -200 to +30 solely by increasing the CdSe shell thickness, demonstrating that strong quantum confinement and wavefunction engineering in heterostructured nanocrystal materials can be used to manipulate carrier-Mn(2+) wavefunction overlap and the sp-d exchange parameters themselves.

The development of nanocrystal quantum dots (NQDs) with suppressed nonradiative Auger recombination has been an important goal in colloidal nanostructure research motivated by the needs of prospective applications in lasing devices, light emitting diodes, and photovoltaic cells. Here, we conduct single-nanocrystal spectroscopic studies of recently developed core-shell NQDs (so-called "giant" NQDs) that comprise a small CdSe core surrounded by a 16-monolayer-thick CdS shell. Using both continuous-wave and pulsed excitation, we observe strong emission features due both to neutral and charged biexcitons, as well as multiexcitons of higher order. The development of pronounced multiexcitonic peaks in steady-state photoluminescence of individual nanocrystals, as well as continuous growth of the emission intensity in the range of high pump levels, point toward a significant suppression of nonradiative Auger decay that normally renders multiexcitons nonemissive. The unusually high multiexciton emission efficiencies in these systems open interesting opportunities for studies of multiexciton phenomena using wellestablished methods of single-dot spectroscopy, as well as new exciting prospects for applications, that have previously been hampered by nonradiative Auger decay.

The electrochemically active area of a proton exchange membrane fuel cell (PEMFC) is investigated using conductive probe atomic force microscopy (CP-AFM). A platinum-coated AFM tip is used as a nanoscale cathode in an operating PEMFC. We present results that show highly inhomogeneous distributions of conductive surface domains at several length scales. At length scales on the order of the aqueous domains of the membrane, approximately 50 nm, we observe single channel electrochemistry. I-V curves for single conducting channels are obtained, which yield insight into the nature of conductive regions across the PEM. In addition, we demonstrate a new characterization technique, phase current correlation microscopy, which gives a direct measure of the electrochemical activity for each aqueous domain. This shows that a large number ( approximately 60%) of the aqueous domains present at the surface of an operating Nafion membrane are inactive. We attribute this to a combination of limited aqueous domain connectivity and catalyst accessibility.

The authors report the optical characteristics of GaSb∕GaAs self-assembled quantum dots (QDs) embedded in an InGaAs quantum well (QW). Variations in the In composition of the QW can significantly alter the emission wavelength up to 1.3μm and emission efficiency. Lasing operation at room temperature is obtained from a 2-mm-long device containing five stacked GaSb QDs in In0.13Ga0.87As QWs at 1.026μm with a threshold current density of 860A∕cm2. The probable lasing transition involves electrons and holes confined in the QW and QDs, respectively, resulting in a large peak modal gain of 45cm−1. A significant blueshift of the electroluminescence peak is observed with increased injection current and suggests a type-II band structure.

We measure the photoluminescence lifetime τ of excitons in colloidal PbSe nanocrystals (NCs) at low temperatures to 270 mK and in high magnetic fields to 15 T. For all NCs, τ increases sharply below 10 K but saturates by 500 mK. In contrast to the usual picture of well-separated "bright" and "dark" exciton states (found, e.g., in CdSe NCs), these dynamics fit remarkably well to a system having two exciton states with comparable--but small--oscillator strengths that are separated by only 300-900  μeV depending on NC size. Importantly, magnetic fields reduce τ below 10 K, consistent with field-induced mixing between the two states. Magnetic-circular dichroism studies reveal exciton g factors from 2-5, and magnetophotoluminescence shows >10% circularly polarized emission.

The spectroscopic and near‐field scanning optical microscopy (NSOM) studies of phosphorescent films doped with colloidal gold nanoparticles (NPs) are presented. Films with a high concentration of 2,3,7,8,12,13,17,18‐octaethyl‐21H,23H‐porphine platinum(II) dispersed in a neutral polymer poly[(methyl methacrylate)‐co‐(ethyl acrylate)] demonstrate a twofold increase of the phosphorescence quantum yield after the addition of aggregated NPs. In materials doped with unaggregated particles, a decrease of the emission yield is observed. Theoretical modeling of the phosphorescence transients suggests a minimization of the triplet–triplet quenching owing to the presence of fast processes that decrease the concentration of chromophores in the excited state and may be both of radiative and non‐radiative origin. NSOM examination of the films reveals increased light emission around large NP clusters. This observation demonstrates significant enhancement of the spontaneous emission rates by the large aggregates, although unaggregated NPs introduce mostly phosphorescence quenching sites.

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