Photoluminescence Enhancement through Symmetry Breaking Induced by Defects in Nanocrystals.

We present a theoretical model for the effect of symmetry breaking introduced by the doping of semiconductor nanocrystals with Coulomb impurities. The presence of a Coulomb center breaks the nanocrystal symmetry and affects its optical properties through the mixing of the hole spin and parity sublevels, breaking the selection rules responsible for the exciton dark state in undoped nanocrystals. After reviewing the effects on the exciton fine structure and optical selection rules using symmetry theory, we present a perturbative model to quantify the effects. We find that the symmetry breaking proceeds by two mechanisms: First, mixing by even parity terms in the Coulomb multipole expansion results in an exciton fine structure consisting of three optically active doublets which are polarized along x, y, and z axes with a ground optically passive dark exciton state, and second, odd parity terms which break inversion symmetry significantly activate optical transitions which are optically forbidden in the unperturbed nanocrystal due to both spin and parity selection rules. In the case of small sized "quasi-spherical" nanocrystals, the introduction of a single positively charged Coulomb center is shown here to result in significant enhancement of the radiative decay rate at room temperatures by up to a factor of 10.

Thermal activation of non-radiative Auger recombination in charged colloidal nanocrystals.

Applications of semiconductor nanocrystals such as biomarkers and light-emitting optoelectronic devices require that their fluorescence quantum yield be close to 100%. However, such quantum yields have not been obtained yet, in part, because non-radiative Auger recombination in charged nanocrystals could not be suppressed completely. Here, we synthesize colloidal core/thick-shell CdSe/CdS nanocrystals with 100% quantum yield and completely quenched Auger processes at low temperatures, although the nanocrystals are negatively photocharged. Single particle and ensemble spectroscopy in the temperature range 30-300 K shows that the non-radiative Auger recombination is thermally activated around 200 K. Experimental results are well described by a model suggesting a temperature-dependent delocalization of one of the trion electrons from the CdSe core and enhanced Auger recombination at the abrupt CdS outer surface. These results point to a route for the design of core/shell structures with 100% quantum yield at room temperature.

Colloidal nanoplatelets with two-dimensional electronic structure.

The syntheses of strongly anisotropic nanocrystals with one dimension much smaller than the two others, such as nanoplatelets, are still greatly underdeveloped. Here, we demonstrate the formation of atomically flat quasi-two-dimensional colloidal CdSe, CdS and CdTe nanoplatelets with well-defined thicknesses ranging from 4 to 11 monolayers. These nanoplatelets have the electronic properties of two-dimensional quantum wells formed by molecular beam epitaxy, and their thickness-dependent absorption and emission spectra are described very well within an eight-band Pidgeon-Brown model. They present an extremely narrow emission spectrum with full-width at half-maximum less than 40 meV at room temperature. The radiative fluorescent lifetime measured in CdSe nanoplatelets decreases with temperature, reaching 1 ns at 6 K, two orders of magnitude less than for spherical CdSe nanoparticles. This makes the nanoplatelets the fastest colloidal fluorescent emitters and strongly suggests that they show a giant oscillator strength transition.

Anomalous circular polarization of photoluminescence spectra of individual CdSe nanocrystals in an applied magnetic field.

We study the low-temperature magnetophotoluminescence from individual CdSe nanocrystals. Nanocrystals having a small "bright" exciton fine structure splitting (Delta_{XY}<0.5 meV) exhibit a conventional left and right circularly polarized Zeeman photoluminescence doublet in applied magnetic fields. In contrast, nanocrystals with large Delta_{XY} (>1 meV) show an anomalous magnetophotoluminescence polarization, wherein the lower-energy peak becomes circularly polarized with increasing field, while the higher-energy peak remains linearly polarized. This unusual behavior arises from strong mixing between the absorbing and emitting bright exciton levels due to strong anisotropic exchange interactions.

Trapped-dopant model of doping in semiconductor nanocrystals.

We propose a framework for describing the impurity doping of semiconductor colloidal nanocrystals. The model is applicable when diffusion of impurities through the nanocrystal is sufficiently small that it can be neglected. In this regime, the incorporation of impurities requires that they stably adsorb on the nanocrystal surface before being overgrown. This adsorption may be preempted by surfactants in the growth solution. We analyze numerically this competition for the case of Mn doping of CdSe nanocrystals. Our model is consistent with recent experiments and offers a route to the rational optimization of doped colloidal nanocrystals.

Nuclei-induced frequency focusing of electron spin coherence.

The hyperfine interaction of an electron with the nuclei is considered as the primary obstacle to coherent control of the electron spin in semiconductor quantum dots. We show, however, that the nuclei in singly charged quantum dots act constructively by focusing the electron spin precession about a magnetic field into well-defined modes synchronized with a laser pulse protocol. In a dot with a synchronized electron, the light-stimulated fluctuations of the hyperfine nuclear field acting on the electron are suppressed. The information about electron spin precession is imprinted in the nuclei and thereby can be stored for tens of minutes in darkness. The frequency focusing drives an electron spin ensemble into dephasing-free subspaces with the potential to realize single frequency precession of the entire ensemble.

Multiexciton generation by a single photon in nanocrystals.

We have theoretically shown that efficient generation of multi-electron-hole pairs by a single photon observed recently in semiconductor nanocrystals1-4 is caused by breaking the single electron approximation for carriers with kinetic energy above the effective energy gap. Due to strong Coulomb interaction, these states form a coherent superposition with charged excitons of the same energy. This concept allows us to define the conditions for dominant two-exciton generations by a single photon: the thermalization rate of a single exciton, initiated by light, should be lower than both the two-exciton state thermalization rate and the rate of Coulomb coupling between single and two exciton states. Possible experimental manifestations of our model are discussed.

Mode locking of electron spin coherences in singly charged quantum dots.

The fast dephasing of electron spins in an ensemble of quantum dots is detrimental for applications in quantum information processing. We show here that dephasing can be overcome by using a periodic train of light pulses to synchronize the phases of the precessing spins, and we demonstrate this effect in an ensemble of singly charged (In,Ga)As/GaAs quantum dots. This mode locking leads to constructive interference of contributions to Faraday rotation and presents potential applications based on robust quantum coherence within an ensemble of dots.

Optical control of spin coherence in singly charged (In,Ga)As/GaAs quantum dots.

Electron spin coherence has been generated optically in n-type modulation doped (In,Ga)As/GaAs quantum dots (QDs) which contain on average a single electron per dot. The coherence arises from resonant excitation of the QDs by circularly polarized laser pulses, creating a coherent superposition of an electron and a trion. Time dependent Faraday rotation is used to probe the spin precession of the optically oriented electrons about a transverse magnetic field. The coherence generation can be controlled by pulse intensity, being most efficient for (2n+1)pi pulses.

Optical pumping of the electronic and nuclear spin of single charge-tunable quantum dots.

We present a comprehensive examination of optical pumping of spins in individual GaAs quantum dots as we change the net charge from positive to neutral to negative with a charge-tunable heterostructure. Negative photoluminescence polarization memory is enhanced by optical pumping of ground state electron spins, which we prove with the first measurements of the Hanle effect on an individual quantum dot. We use the Overhauser effect in a high longitudinal magnetic field to demonstrate efficient optical pumping of nuclear spins for all three charge states of the quantum dot.

Orbital mechanisms of electron-spin manipulation by an electric field.

A theory of spin manipulation of quasi-two-dimensional (2D) electrons by a time-dependent gate voltage applied to a quantum well is developed. The Dresselhaus and Rashba spin-orbit coupling mechanisms are shown to be rather efficient for this purpose. The spin response to a perpendicular-to-plane electric field is due to a deviation from the strict 2D limit and is controlled by the ratios of the spin, cyclotron, and confinement frequencies. The dependence of this response on the magnetic field direction is indicative of the strengths of the competing spin-orbit coupling mechanisms.

Manipulation of the spin memory of electrons in n-GaAs.

We report on the optical manipulation of the electron spin relaxation time in a GaAs-based heterostructure. Experimental and theoretical study shows that the average electron spin relaxes through hyperfine interaction with the lattice nuclei, and that the rate can be controlled by electron-electron interactions. This time has been changed from 300 ns down to 5 ns by variation of the laser frequency. This modification originates in the optically induced depletion of an n-GaAs layer.