Controlling photoinduced electron transfer from PbS@CdS core@shell quantum dots to metal oxide nanostructured thin films.

N-type metal oxide solar cells sensitized by infrared absorbing PbS quantum dots (QDs) represent a promising alternative to traditional photovoltaic devices. However, colloidal PbS QDs capped with pure organic ligand shells suffer from surface oxidation that affects the long term stability of the cells. Application of a passivating CdS shell guarantees the increased long term stability of PbS QDs, but can negatively affect photoinduced charge transfer from the QD to the oxide and the resulting photoconversion efficiency (PCE). For this reason, the characterization of electron injection rates in these systems is very important, yet has never been reported. Here we investigate the photoelectron transfer rate from PbS@CdS core@shell QDs to wide bandgap semiconducting mesoporous films using photoluminescence (PL) lifetime spectroscopy. The different electron affinity of the oxides (SiO2, TiO2 and SnO2), the core size and the shell thickness allow us to fine tune the electron injection rate by determining the width and height of the energy barrier for tunneling from the core to the oxide. Theoretical modeling using the semi-classical approximation provides an estimate for the escape time of an electron from the QD 1S state, in good agreement with experiments. The results demonstrate the possibility of obtaining fast charge injection in near infrared (NIR) QDs stabilized by an external shell (injection rates in the range of 110-250 ns for TiO2 films and in the range of 100-170 ns for SnO2 films for PbS cores with diameters in the 3-4.2 nm range and shell thickness around 0.3 nm), with the aim of providing viable solutions to the stability issues typical of NIR QDs capped with pure organic ligand shells.

Confinement and interaction of single indirect excitons in a voltage-controlled trap formed inside double InGaAs quantum Wells.

Voltage-tunable quantum traps confining individual spatially indirect and long-living excitons are realized by providing a coupled double quantum well with nanoscale gates. This enables us to study the transition from confined multiexcitons down to a single, electrostatically trapped indirect exciton. In the few exciton regime, we observe discrete emission lines identified as resulting from a single dipolar exciton, a biexciton, and a triexciton, respectively. Their energetic splitting is well described by Wigner-like molecular structures reflecting the interplay of dipolar interexcitonic repulsion and spatial quantization.

Aharonov-Bohm excitons at elevated temperatures in type-II ZnTe/ZnSe quantum dots.

Optical emission from type-II ZnTe/ZnSe quantum dots demonstrates large and persistent oscillations in both the peak energy and intensity indicating the formation of coherently rotating states. Furthermore, these Aharonov-Bohm oscillations are shown to be remarkably robust and persist until 180 K. This is at least one order of magnitude greater than the typical temperatures in lithographically defined rings. To our knowledge, this is the highest temperature at which the AB effect has been observed in solid-state and molecular nanostructures.

Optically induced hybridization of a quantum dot state with a filled continuum.

We present an optical signature of a hybridization between a localized quantum dot state and a filled continuum. Radiative recombination of the negatively charged trion in a single quantum dot leaves behind a single electron. We show that in two regions of vertical electric field, the electron hybridizes with a continuum through a tunneling interaction. The hybridization manifests itself through an unusual voltage dependence of the emission energy and a non-Lorentzian line shape, features which we reproduce with a theory based on the Anderson Hamiltonian.

The nonlinear Fano effect.

The Fano effect is ubiquitous in the spectroscopy of, for instance, atoms, bulk solids and semiconductor heterostructures. It arises when quantum interference takes place between two competing optical pathways, one connecting the energy ground state and an excited discrete state, the other connecting the ground state with a continuum of energy states. The nature of the interference changes rapidly as a function of energy, giving rise to characteristically asymmetric lineshapes. The Fano effect is particularly important in the interpretation of electronic transport and optical spectra in semiconductors. Whereas Fano's original theory applies to the linear regime at low power, at higher power a laser field strongly admixes the states and the physics becomes rich, leading, for example, to a remarkable interplay of coherent nonlinear transitions. Despite the general importance of Fano physics, this nonlinear regime has received very little attention experimentally, presumably because the classic autoionization processes, the original test-bed of Fano's ideas, occur in an inconvenient spectral region, the deep ultraviolet. Here we report experiments that access the nonlinear Fano regime by using semiconductor quantum dots, which allow both the continuum states to be engineered and the energies to be rescaled to the near infrared. We measure the absorption cross-section of a single quantum dot and discover clear Fano resonances that we can tune with the device design or even in situ with a voltage bias. In parallel, we develop a nonlinear theory applicable to solid-state systems with fast relaxation of carriers. In the nonlinear regime, the visibility of the Fano quantum interferences increases dramatically, affording a sensitive probe of continuum coupling. This could be a unique method to detect weak couplings of a two-level quantum system (qubits), which should ideally be decoupled from all other states.

Voltage control of the spin dynamics of an exciton in a semiconductor quantum dot.

We report the observation of a spin-flip process in a quantum dot whereby a dark exciton with total angular momentum L = 2 becomes a bright exciton with L = 1. The spin-flip process is revealed in the decay dynamics following nongeminate excitation. We are able to control the spin-flip rate by more than an order of magnitude simply with a dc voltage. The spin-flip mechanism involves a spin exchange with the Fermi sea in the back contact of our device and corresponds to the high temperature Kondo regime. We use the Anderson Hamiltonian to calculate a spin-flip rate, and we find excellent agreement with the experimental results.

Decoherence of rabi oscillations in a single quantum dot.

We develop a realistic model of Rabi oscillations in a quantum-dot photodiode. Based in a multiexciton density matrix formulation we show that for short pulses the two-level model fails and higher levels should be taken into account. This affects some of the experimental conclusions, such as the inferred efficiency of the state rotation (population inversion) and the deduced value of the dipole interaction. We also show that the damping observed cannot be explained using constant rates with fixed pulse duration. We demonstrate that the damping observed is in fact induced by an off-resonant excitation to or from the continuum of wetting layer states. Our model describes the nonlinear decoherence behavior observed in recent experiments.

Aharonov-Bohm signature for neutral polarized excitons in type-II quantum dot ensembles.

The Aharonov-Bohm effect is commonly believed to be a typical feature of the motion of a charged particle interacting with the electromagnetic vector potential. Here we present a magnetophotoluminescence study of type-II InP/GaAs self-assembled quantum dots, revealing the Aharonov-Bohm-type oscillations for neutral excitons when the hole ground state changes its angular momentum from l(h)=0 to l(h)=1, 2, and 3. The hole-ring parameters derived from a simple model are in excellent agreement with the structural parameters for this system.

Nonlinear charge spreading visualized in voltage-controlled lateral superlattices.

Voltage-controlled lateral potential superlattices are used to dramatically increase the lifetime of photogenerated carriers in a quantum well. These long lifetimes, together with the ability to deliberately trigger radiative recombination, enable us to directly visualize the spreading character of nonlinear Maxwell relaxation of 2D charges along narrow channels. Our system allows for temporal and spatial resolution of Maxwell kinetics, usually a very fast process and difficult to observe. The observed spreading dynamics of a 2D hole plasma is in perfect agreement with our nonlinear model.

Self-induced acoustic transparency in semiconductor quantum films.

We develop a quantum theory of the nonlinear interaction between intense surface acoustic waves and electrons in a quantum well in the regime of moving quantum wires and dots. In the quantum nonlinear regime, the sound attenuation exhibits quantum oscillations and dramatically decreases with increasing quantization. In the case of dynamically created electron dots formed by two acoustic waves, the waves can propagate without any dissipation in the limit of high sound intensity and, hence, the electron quantum film acts as an acoustically quasitransparent material.

Spectroscopy of nanoscopic semiconductor rings.

Making use of self-assembly techniques, we realize nanoscopic semiconductor quantum rings in which the electronic states are in the true quantum limit. We employ two complementary spectroscopic techniques to investigate both the ground states and the excitations of these rings. Applying a magnetic field perpendicular to the plane of the rings, we find that, when approximately one flux quantum threads the interior of each ring, a change in the ground state from angular momentum l = 0 to l = -1 takes place. This ground state transition is revealed both by a drastic modification of the excitation spectrum and by a change in the magnetic-field dispersion of the single-electron charging energy.