Spectral diffusion of single semiconductor nanocrystals: the influence of the dielectric environment

We have explored the influence of different matrices on the emission line shape of individual homogeneously coated CdSe/CdS/ZnS nanocrystals. The results obtained corroborate previous observations of a correlation between blinking events and spectral diffusion but in addition we have found that the extent of spectral diffusion is almost independent of the dielectric environment of the NC. Additionally, we report the observation of a correlation between the line width and emission energy which is not expected to occur in the spherical - symmetric NCs employed in this work. The implications of these results are discussed.Comment: 3 pages, 3 figure

Hot Carrier extraction with plasmonic broadband absorbers

Hot charge carrier extraction from metallic nanostructures is a very promising approach for applications in photo-catalysis, photovoltaics and photodetection. One limitation is that many metallic nanostructures support a single plasmon resonance thus restricting the light-to-charge-carrier activity to a spectral band. Here we demonstrate that a monolayer of plasmonic nanoparticles can be assembled on a multi-stack layered configuration to achieve broad-band, near-unit light absorption, which is spatially localised on the nanoparticle layer. We show that this enhanced light absorbance leads to $\sim$ 40-fold increases in the photon-to-electron conversion efficiency by the plasmonic nanostructures. We developed a model that successfully captures the essential physics of the plasmonic hot-electron charge generation and separation in these structures. This model also allowed us to establish that efficient hot carrier extraction is limited to spectral regions where the photons possessing energies higher than the Schottky junctions and the localised light absorption of the metal nanoparticles overlap.Comment: submitte

Transparent metal electrodes from ordered nanosphere arrays

We show that perforated metal electrode arrays, fabricated using nanosphere lithography, provide a viable alternative to conductive metal oxides as transparent electrode materials. The inter-aperture spacing is tuned by varying etching times in an oxygen plasma, and the effect of inter-aperture “wire” thickness on the optical and electronic properties of perforated silver films is shown. Optical transmission is limited by reflection and surface plasmons, and for these results do not exceed 73%. Electrical sheet resistance is shown to be as low as 3 Ω ◻−1 for thermally evaporated silver films. The performance of organic photovoltaic devices comprised of a P3HT:PCBM bulk heterojunction deposited onto perforated metal arrays is shown to be limited by optical transmission, and a simple model is presented to overcome these limitations

Scanning nano-spin ensemble microscope for nanoscale magnetic and thermal imaging

Quantum sensors based on solid-state spins provide tremendous opportunities in a wide range of fields from basic physics and chemistry to biomedical imaging. However, integrating them into a scanning probe microscope to enable practical, nanoscale quantum imaging is a highly challenging task. Recently, the use of single spins in diamond in conjunction with atomic force microscopy techniques has allowed significant progress towards this goal, but generalisation of this approach has so far been impeded by long acquisition times or by the absence of simultaneous topographic information. Here we report on a scanning quantum probe microscope which solves both issues, by employing a nano-spin ensemble hosted in a nanodiamond. This approach provides up to an order of magnitude gain in acquisition time, whilst preserving sub-100 nm spatial resolution both for the quantum sensor and topographic images. We demonstrate two applications of this microscope. We first image nanoscale clusters of maghemite particles through both spin resonance spectroscopy and spin relaxometry, under ambient conditions. Our images reveal fast magnetic field fluctuations in addition to a static component, indicating the presence of both superparamagnetic and ferromagnetic particles. We next demonstrate a new imaging modality where the nano-spin ensemble is used as a thermometer. We use this technique to map the photo-induced heating generated by laser irradiation of a single gold nanoparticle in a fluid environment. This work paves the way towards new applications of quantum probe microscopy such as thermal/magnetic imaging of operating microelectronic devices and magnetic detection of ion channels in cell membranes.Comment: 22 pages including Supporting Information. Changes to v1: affiliations and funding information updated, plus minor revisions to the main tex

Charge hopping revealed by jitter correlations in the photoluminescence spectra of single CdSe nanocrystals

Spectral fluctuations observed in single CdSe/ZnS nanocrystals at 5 K are found to be entirely the result of discrete charge hops in the local environment of the nanocrystal, which occur at a rate comparable to the acquisition time of a single spectrum. We show that intervals between discrete spectral hops introduce a correlation between the successive measurements of the emission wavelength of single CdSe nanocrystals. This correlation can be recovered even in the presence of noise, but is shown to be sensitive to the experimental acquisition time, in good agreement with theory. However, we only find correlations for the smaller of the two nanocrystal sizes studied and discuss this in terms of size-dependent time scales correlated with the amount of excess energy dissipated in the nanocrystal due to hot-carrier relaxation. © 2010 The American Physical Societ

Anomalous power laws of spectral diffusion in quantum dots: A connection to luminescence intermittency

We show that the wandering of transition frequencies in colloidal quantum dots does not follow the statistics expected for ordinary diffusive processes. The trajectory of this anomalous spectral diffusion is characterized by a root t dependence of the squared deviation. The behavior is reproduced when the electronic states of quantum dots are assumed to interact with environments such as, for example, an ensemble of two-level systems, where the correlation times are distributed according to a power law similar to the one generally attributed to the dot's luminescence intermittency

Inertial Imaging with Nanomechanical Systems

Mass sensing with nanoelectromechanical systems has advanced significantly during the last decade. With nanoelectromechanical systems sensors it is now possible to carry out ultrasensitive detection of gaseous analytes, to achieve atomic-scale mass resolution and to perform mass spectrometry on single proteins. Here, we demonstrate that the spatial distribution of mass within an individual analyte can be imaged—in real time and at the molecular scale—when it adsorbs onto a nanomechanical resonator. Each single-molecule adsorption event induces discrete, time-correlated perturbations to all modal frequencies of the device. We show that by continuously monitoring a multiplicity of vibrational modes, the spatial moments of mass distribution can be deduced for individual analytes, one-by-one, as they adsorb. We validate this method for inertial imaging, using both experimental measurements of multimode frequency shifts and numerical simulations, to analyse the inertial mass, position of adsorption and the size and shape of individual analytes. Unlike conventional imaging, the minimum analyte size detectable through nanomechanical inertial imaging is not limited by wavelength-dependent diffraction phenomena. Instead, frequency fluctuation processes determine the ultimate attainable resolution. Advanced nanoelectromechanical devices appear capable of resolving molecular-scale analytes

On the age of the hominid fossils at the Sima de los Huesos, Sierra de Atapuerca, Spain: paleomagnetic evidence

We report new paleomagnetic data for the Middle Pleistocene hominid-bearing strata in the Sima de los Huesos, North Spain. Sediments (brown muds with human and bear fossils and the underlying sterile clayey and sandy unit) preserve both normal and reversed magnetic components. The sterile unit has exclusively reversed magnetization, dating back to the Matuyama Chron, and thus is Lower Pleistocene in age. The overlying fossiliferous muds have a dominant normal magnetization that overprints a partially resolved reversed magnetization. These data are compatible with one of the reversal events that occurred during the Brunhes Chron. Combined with the existing U-series dates and evidence from the macro- and microfauna, these paleomagnetic results suggest an age of the hominid fossils between 325 to 205 ka, whereas the underlying sand and silts are older than 780 ka.This research was supported by DGES grants PB96-0815 and PB96-1026-C03, and by the Unidad Asociada CSIC-UCM.Peer reviewe

On the colloidal stability of apolar nanoparticles: The role of particle size and ligand shell structure

Being able to predict and tune the colloidal stability of nanoparticles is essential for a wide range of applications, yet our ability to do so is currently poor due to a lack of understanding of how they interact with one another. Here, we show that the agglomeration of apolar particles is dominated by either the core or the ligand shell, depending on the particle size and materials. We do this by using Small-Angle X-ray Scattering and molecular dynamics simulations to characterize the interaction between hexadecanethiol passivated gold nanoparticles in decane solvent. For smaller particles, the agglomeration temperature and interparticle spacing are determined by ordering of the ligand shell into bundles of aligned ligands that attract one another and interlock. In contrast, the agglomeration of larger particles is driven by van der Waals attraction between the gold cores, which eventually becomes strong enough to compress the ligand shell. Our results provide a microscopic description of the forces that determine the colloidal stability of apolar nanoparticles and explain why classical colloid theory fails.Comment: 26 pages, 4 figures, plus S