Single-charge transport through hybrid core-shell Au-ZnS quantum dots: a comprehensive analysis from a modified energy structure.

We examined the modified electronic structure and single-carrier transport of individual hybrid core-shell metal-semiconductor Au-ZnS quantum dots (QDs) using a scanning tunnelling microscope. Nearly monodisperse ultra-small QDs are achieved by a facile wet chemical route. The exact energy structures are evaluated by scanning tunnelling spectroscopy (STS) measurements at 300 mK for the individual nanoobjects starting from the main building block Au nanocrystals (NCs) to the final Au-ZnS QDs. The study divulges the evolution of the energy structure and the charge transport from the single metallic building block core to the core-shell metal-semiconductor QDs. Furthermore, we successfully determined the contributions related to the quantum-confinement-induced excitonic band structure of the ZnS nano-shell and the charging energy of the system by applying a semi-empirical approach considering a double barrier tunnel junction (DBTJ) arrangement. We detect strong conductance peaks in Au-ZnS QDs due to the overlapping of the energy structure of the Au nano-core and the discrete energy states of the semiconductor ZnS nano-shell. Our findings will help in understanding the electronic properties of metal-semiconductor QDs. The outcomes therefore have the potential to fabricate tailored metal-semiconductor QDs for single-electron devices.

Energy scales and dynamics of electronic excitations in functionalized gold nanoparticles measured at the single particle level.

The knowledge of the electronic structure and dynamics of nanoparticles is a prerequisite to develop miniaturized single-electron devices based on nanoparticles. Low-temperature transport measurements of individual stable metallic nanoparticles enable unravelling the system specific electronic structure while ultrafast optical spectroscopy gives access to the electron dynamics. In this work, we investigate bare and thiol-functionalized gold nanoparticles. For the latter, we employ a fast and low-cost fabrication technique which yields nanoparticles with narrow size distribution. Using relatively long thiol-ended alkane chains for the functionalization modifies the electronic density of states of the nanoparticles. The study of decay dynamics of surface-plasmon-related hot electrons reveals the presence of electronic states at the interface which serve as a fast decay channel for electronic relaxation. By low-temperature scanning tunnelling microscopy we precisely investigate the energy scales and electronic interactions relevant for the tunnel charge transport through this system. We observe that the interaction between the functional ligand and the substrate on which the nanoparticles reside also influences the electronic transport. The procedure that we employ can be easily adapted to other metallic nanoparticles. Our findings are therefore important for incorporating them into single-electron devices.

Single-electron transport through stabilised silicon nanocrystals.

We have fabricated organically capped stable luminescent silicon nanocrystals with narrow size distribution by a novel, high yield and easy to implement technique. We demonstrate transport measurements of individual silicon nanocrystals by scanning tunnelling microscopy at a low temperature in a double-barrier tunnel junction arrangement in which we observed pronounced single electron tunnelling effects. The tunnelling spectroscopy of these nanocrystals with different diameters reveals quantum confinement induced bandgap modifications. Furthermore, from the features in the tunnelling spectra, we differentiate several energy contributions arising from electronic interactions inside the nanocrystal. By applying a magnetic field, we have detected a variation in the differential conductance profile that we attribute to arising from higher order tunnelling processes. We have also systematically simulated our experimental data with the Orthodox theory, and the results show good agreement with the experiment. The study establishes a correlation between the nanocrystal size and quantum confinement induced band-structure modifications which will pave the way to devise tailored nanocrystals.

Highly lattice-mismatched semiconductor-metal hybrid nanostructures: gold nanoparticle encapsulated luminescent silicon quantum dots.

Synthesis of hybrid core-shell nanostructures requires moderate lattice mismatch (<5%) between the materials of the core and the shell and usually results in the formation of structures with an atomically larger entity comprising the core. A reverse situation, where an atomically larger entity encapsulates a smaller atomic radius component having substantial lattice mismatch is unachievable by conventional growth techniques. Here, we report successful synthesis of ultra-small, light-emitting Si quantum dots (QDs) encapsulated by Au nanoparticles (NPs) forming a hybrid nanocomposite that exhibits intense room temperature photoluminescence (PL) and intriguing plasmon-exciton coupling. A facile strategy was adopted to utilize the active surface of oxide etched Si QDs as preferential sites for Au NP nucleation and growth which resulted in the formation of core-shell nanostructures consisting of an atomically smaller Si QD core surrounded by a substantially lattice-mismatched Au NP shell. The PL characteristics of the luminescent Si QDs (quantum yield ∼28%) are dramatically altered following Au NP encapsulation. Au coverage of the bare Si QDs effectively stabilizes the emission spectrum and leads to a red-shift of the PL maxima by ∼37 nm. The oxide related PL peaks observed in Si QDs are absent in the Au treated sample suggesting the disappearance of oxide states and the appearance of Au NP associated Stark shifted interface states within the widened band-gap of the Si QDs. Emission kinetics of the hybrid system show accelerated decay due to non-radiative energy transfer between the Si QDs and the Au NPs and associated quenching in PL efficiency. Nevertheless, the quantum yield of the hybrid remains high (∼20%) which renders these hetero-nanostructures exciting candidates for multifarious applications.