We report ultra-efficient multiple exciton generation (MEG) for single photon absorption in colloidal PbSe and PbS quantum dots (QDs). We employ transient absorption spectroscopy and present measurement data acquired for both intraband as well as interband probe energies. Quantum yields of 300% indicate the creation, on average, of three excitons per absorbed photon for PbSe QDs at photon energies that are four times the QD energy gap. Results indicate that the threshold photon energy for MEG in QDs is twice the lowest exciton absorption energy. We find that the biexciton effect, which shifts the transition energy for absorption of a second photon, influences the early time transient absorption data and may contribute to a modulation observed when probing near the lowest interband transition. We present experimental and theoretical values of the size-dependent interband transition energies for PbSe QDs. We present experimental and theoretical values of the size-dependent interband transition energies for PbSe QDs, and we also introduce a new model for MEG based on the coherent superposition of multiple excitonic states.

Nanostructured semiconductors emit light from electronic states known as excitons. For organic materials, Hund's rules state that the lowest-energy exciton is a poorly emitting triplet state. For inorganic semiconductors, similar rules predict an analogue of this triplet state known as the 'dark exciton'. Because dark excitons release photons slowly, hindering emission from inorganic nanostructures, materials that disobey these rules have been sought. However, despite considerable experimental and theoretical efforts, no inorganic semiconductors have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in caesium lead halide perovskites (CsPbX, with X = Cl, Br or I) involves a highly emissive triplet state. We first use an effective-mass model and group theory to demonstrate the possibility of such a state existing, which can occur when the strong spin-orbit coupling in the conduction band of a perovskite is combined with the Rashba effect. We then apply our model to CsPbX nanocrystals, and measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright triplet character of the lowest exciton explains the anomalous photon-emission rates of these materials, which emit about 20 and 1,000 times faster than any other semiconductor nanocrystal at room and cryogenic temperatures, respectively. The existence of this bright triplet exciton is further confirmed by analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals, which are already used in lighting, lasers and displays, these excitons could lead to materials with brighter emission. More generally, our results provide criteria for identifying other semiconductors that exhibit bright excitons, with potential implications for optoelectronic devices.

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.

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.

We have theoretically shown that optical properties of semiconductor nanorods are controlled by 1D excitons. The theory, which takes into account anisotropy of spacial and dielectric confinement, describes size dependence of interband optical transitions, exciton binding energies. We have demonstrated that the fine structure of the ground exciton state explains the linear polarization of photoluminescence. Our results are in good agreement with the measurements in CdSe nanorods.PACS numbers: 71.70.Gm, 77.22.Ej There is growing interest in nano-size crystalline semiconductor structures of various shapes such as nanocrystals (NCs) [1], nanorods (NRs) [2] and nanowires (NWs) [3] created by the "from the bottom up" technological approach. Size-tunable control of their optical and transport properties combined with the ability to move these nano-size objects around with precise control opens the exciting possibilities for the creation of new functional materials which can be used in unlimited applications. Among these nanostructures, the NCs are the most heavily studied and one can find a broad description of their properties and their potential applications in the reviews of Brus [4] and Alivisatos [5].The optical properties of NRs, however, differ significantly from those of NCs. Compared to NCs, the NRs show higher photoluminescence (PL) quantum efficiency [2], strongly linear polarized PL [6,7], an increase of the global Stokes shift [6], and significantly faster carrier relaxation [8]. The Auger processes in NRs are strongly suppressed relative to those in NCs [9,10], which subsequently decreases the optical pumping threshold for stimulated emission [10,11]. The size and shape dependence of the optical and tunneling gaps measured in CdSe NRs [12] shows an unexpectedly large difference that cannot be explained by the electron-hole Coulomb correction to the optical gap used for NCs. To describe their measurements Katz et al.[12] applied the four-band theory developed by Sercel and Vahala [13]. The most important result of the latter paper was the prediction of an inverse order of light and heavy hole subbands in NWs, which was later confirmed by semiempirical pseudopotential calculations [6,14,15] and numerical calculations within the 6 band model [16]. An anisotropy of the light hole-toelectron optical transition matrix element predicts some degree of the PL linear polarization parallel to the NW [17,18].The dielectric confinement connected with the difference between dielectric constants of semiconductor crystallites, κ s , and surrounding medium, κ m , (for example, see [19]) usually does not affect the optical spectra of NCs because the charge distributions of an excited electron and hole practically compensate each other at each point of the NC. This leads to a complete screening of an electric field of the total charge from penetration into the surrounding medium. This is not the case, however, in NRs where the electron and hole are at a distance larger than a NR radius and interact predominantly throu...

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.

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.

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.