Daniel Vanmaekelbergh

Photoelectrochemistry of electrodeposited Cu{sub 2}O

The photoelectrochemical properties of electrodeposited Cu{sub 2}O in aqueous solutions were investigated. The material showed long term stability under illumination at negative potentials. The diffusion length of electrons in the as-deposited material was of the order of 10--100 nm. The authors did not observe photocathodic reduction of water. The efficiencies for the reduction of oxygen and the methylviologen cation at these electrodes were surprisingly high. This suggests that, in conjunction with a suitable redox system, electrodeposited Cu{sub 2}O could be a promising material as a p-type photoelectrode in an electrochemical photovoltaic cell.

Long-range orientation and atomic attachment of nanocrystals in 2D honeycomb superlattices

Nanoparticle lattices and surfaces The challenge of resolving the details of the surfaces or assemblies of colloidal semiconductor nanoparticles can be overcome if several characterization methods are used (see the Perspective by Boles and Talapin). Boneschanscher et al. examined honeycomb superlattices of lead selenide nanocrystals formed by the bonding of crystal faces using several methods, including high-resolution electron microscopy and tomography. The structure had octahedral symmetry with the nanocrystals distorted through “necking”: the expansion of the contact points between the nanocrystals. Zherebetskyy et al. used a combination of theoretical calculations and spectroscopic methods to study the surface layer of lead sulfide nanocrystals synthesized in water. In addition to the oleic acid groups that capped the nanocrystals, hydroxyl groups were present as well. Science, this issue p. 1377, p. 1380; see also p. 1340 Metal-chalcogenide nanocrystals undergo necking and large-scale atomic rearrangements when forming a surface lattice. [Also see Perspective by Boles and Talapin] Oriented attachment of synthetic semiconductor nanocrystals is emerging as a route for obtaining new semiconductors that can have Dirac-type electronic bands such as graphene, but also strong spin-orbit coupling. The two-dimensional (2D) assembly geometry will require both atomic coherence and long-range periodicity of the superlattices. We show how the interfacial self-assembly and oriented attachment of nanocrystals results in 2D metal chalcogenide semiconductors with a honeycomb superlattice. We present an extensive atomic and nanoscale characterization of these systems using direct imaging and wave scattering methods. The honeycomb superlattices are atomically coherent and have an octahedral symmetry that is buckled; the nanocrystals occupy two parallel planes. Considerable necking and large-scale atomic motion occurred during the attachment process.

Paramagnetic Lipid-Coated Silica Nanoparticles with a Fluorescent Quantum Dot Core : A New Contrast Agent Platform for Multimodality Imaging

Silica particles as a nanoparticulate carrier material for contrast agents have received considerable attention the past few years, since the material holds great promise for biomedical applications. A key feature for successful application of this material in vivo is biocompatibility, which may be significantly improved by appropriate surface modification. In this study, we report a novel strategy to coat silica particles with a dense monolayer of paramagnetic and PEGylated lipids. The silica nanoparticles carry a quantum dot in their center and are made target-specific by the conjugation of multiple alphavbeta3-integrin-specific RGD-peptides. We demonstrate their specific uptake by endothelial cells in vitro using fluorescence microscopy, quantitative fluorescence imaging, and magnetic resonance imaging. The lipid-coated silica particles introduced here represent a new platform for nanoparticulate multimodality contrast agents.

ZnO nanowire lasers

The pathway towards the realization of optical solid-state lasers was gradual and slow. After Einsteins paper on absorption and stimulated emission of light in 1917 it took until 1960 for the first solid state laser device to see the light. Not much later, the first semiconductor laser was demonstrated and lasing in the near UV spectral range from ZnO was reported as early as 1966. The research on the optical properties of ZnO showed a remarkable revival since 1995 with the demonstration of room temperature lasing, which was further enhanced by the first report of lasing by a single nanowire in 2001. Since then, the research focussed increasingly on one-dimensional nanowires of ZnO. We start this review with a brief description of the opto-electronic properties of ZnO that are related to the wurtzite crystal structure. How these properties are modified by the nanowire geometry is discussed in the subsequent sections, in which we present the confined photon and/or polariton modes and how these can be investigated experimentally. Next, we review experimental studies of laser emission from single ZnO nanowires under different experimental conditions. We emphasize the special features resulting from the sub-wavelength dimensions by presenting our results on single ZnO nanowires lying on a substrate. At present, the mechanism of lasing in ZnO (nanowires) is the subject of a strong debate that is considered at the end of this review.

Statistical analysis of time-resolved emission from ensembles of semiconductor quantum dots: Interpretation of exponential decay models

We present a statistical analysis of time-resolved spontaneous emission decay curves from ensembles of emitters, such as semiconductor quantum dots, with the aim of interpreting ubiquitous non-single-exponential decay. Contrary to what is widely assumed, the density of excited emitters and the intensity in an emission decay curve are not proportional, but the density is a time integral of the intensity. The integral relation is crucial to correctly interpret non-single-exponential decay. We derive the proper normalization for both a discrete and a continuous distribution of rates, where every decay component is multiplied by its radiative decay rate. A central result of our paper is the derivation of the emission decay curve when both radiative and nonradiative decays are independently distributed. In this case, the well-known emission quantum efficiency can no longer be expressed by a single number, but is also distributed. We derive a practical description of non-single-exponential emission decay curves in terms of a single distribution of decay rates; the resulting distribution is identified as the distribution of total decay rates weighted with the radiative rates. We apply our analysis to recent examples of colloidal quantum dot emission in suspensions and in photonic crystals, and we find that this important class of emitters is well described by a log-normal distribution of decay rates with a narrow and a broad distribution, respectively. Finally, we briefly discuss the Kohlrausch stretched-exponential model, and find that its normalization is ill defined for emitters with a realistic quantum efficiency of less than 100%.

Electron-conducting quantum dot solids: novel materials based on colloidal semiconductor nanocrystals

We review the optical and electrical properties of solids that are composed of semiconductor nanocrystals. Crystals, with dimensions in the nanometre range, of II-VI, IV-VI and III-V compound semiconductors, can be prepared by wet-chemical methods with a remarkable control of their size and shape, and surface chemistry. In the uncharged ground state, such nanocrystals are insulators. Electrons can be added, one by one, to the conduction orbitals, forming artificial atoms strongly confined in the nanocrystal. Semiconductor nanocrystals form the building blocks for larger architectures, which self-assemble due to van der Waals interactions. The electronic structure of the quantum dot solids prepared in such a way is determined by the orbital set of the nanocrystal building blocks and the electronic coupling between them. The opto-electronic properties are dramatically altered by electron injection into the orbitals. We discuss the optical and electrical properties of quantum dot solids in which the electron occupation of the orbitals is controlled by the electrochemical potential.

Frequency-Dependent Spontaneous Emission Rate from CdSe and CdTe Nanocrystals: Influence of Dark States

We studied the rate of spontaneous emission from colloidal CdSe and CdTe nanocrystals at room temperature. The decay rate, obtained from luminescence decay curves, increases with the emission frequency in a supralinear way. This dependence is explained by the thermal occupation of dark exciton states at room temperature, giving rise to a strong attenuation of the rate of emission. The supralinear dependence is in agreement with the results of tight-binding calculations.

Morphology and Strongly Enhanced Photoresponse of GaP Electrodes Made Porous by Anodic Etching

Single crystalline n-type GaP was made porous by anodic etching in the dark in sulfuric acid solution. The morphology and (photo)electrochemical properties of the porous layer were investigated. Submicron pits 10 to 30 {micro}m apart were formed at the surface. Below the surface, the pits acted as the nuclei of distinct porous domains. Pore widths and pore wall thicknesses were approximately 100 nm. The creation of the porous layer caused the quantum yield for light-to-current conversion to increase from extremely low values to unity for light absorbed in the indirect optical transition. The mechanism of pore formation and the striking opto-electrical properties of porous GaP are discussed.

Entropy-Driven Formation of Binary Semiconductor-Nanocrystal Superlattices

One of the main reasons for the current interest in colloidal nanocrystals is their propensity to form superlattices, systems in which (different) nanocrystals are in close contact in a well-ordered three-dimensional (3D) geometry resulting in novel material properties. However, the principles underlying the formation of binary nanocrystal superlattices are not well understood. Here, we present a study of the driving forces for the formation of binary nanocrystal superlattices by comparing the formed structures with full free energy calculations. The nature (metallic or semiconducting) and the size-ratio of the two nanocrystals are varied systematically. With semiconductor nanocrystals, self-organization at high temperature leads to superlattices (AlB(2), NaZn(13), MgZn(2)) in accordance with the phase diagrams for binary hard-sphere mixtures; hence entropy increase is the dominant driving force. A slight change of the conditions results in structures that are energetically stabilized. This study provides rules for the rational design of 3D nanostructured binary semiconductors, materials with promises in thermoelectrics and photovoltaics and which cannot be reached by any other technology.

Cu2O: a catalyst for the photochemical decomposition of water?

The photoelectrochemical properties of polycrystalline Cu2O electrodes are discussed with regard to the application of the oxide as a photocatalytic material for water splitting.