We present a theoretical analysis of the band-edge exciton structure in nanometer-size crystallites of direct semiconductors with a cubic lattice structure or a hexagonal lattice structure which can be described within the framework of a quasicubic model. The lowest energy exciton, eightfold degenerate in spherically symmetric dots, is split into five levels by the crystal shape asymmetry, the intrinsic crystal field ͑in hexagonal lattice structures͒, and the electron-hole exchange interaction. Transition oscillator strengths and the size dependence of the splittings have been calculated. Two of the five states, including the ground state, are optically passive ͑dark excitons͒. The oscillator strengths of the other three levels ͑bright excitons͒ depend strongly on crystal size, shape, and energy band parameters. The relative ordering of the energy levels is also heavily influenced by these parameters. The distance between the first optically active state and the optically forbidden ground exciton state increases with decreasing size, leading to an increase of the Stokes shift in the luminescence. Our results are in good agreement with the size dependence of Stokes shifts obtained in fluorescence line narrowing and photoluminescence experiments in CdSe nanocrystals. Mixing of the dark and bright excitons in an external magnetic field allows the direct optical recombination of the dark exciton ground state. The observed shortening of the luminescence decay time in CdSe nanoncrystals in a magnetic field is also in excellent agreement with the theory, giving further support to the validity of our model. ͓S0163-1829͑96͒05831-6͔

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.

Doping--the intentional introduction of impurities into a material--is fundamental to controlling the properties of bulk semiconductors. This has stimulated similar efforts to dope semiconductor nanocrystals. Despite some successes, many of these efforts have failed, for reasons that remain unclear. For example, Mn can be incorporated into nanocrystals of CdS and ZnSe (refs 7-9), but not into CdSe (ref. 12)--despite comparable bulk solubilities of near 50 per cent. These difficulties, which have hindered development of new nanocrystalline materials, are often attributed to 'self-purification', an allegedly intrinsic mechanism whereby impurities are expelled. Here we show instead that the underlying mechanism that controls doping is the initial adsorption of impurities on the nanocrystal surface during growth. We find that adsorption--and therefore doping efficiency--is determined by three main factors: surface morphology, nanocrystal shape, and surfactants in the growth solution. Calculated Mn adsorption energies and equilibrium shapes for several nanocrystals lead to specific doping predictions. These are confirmed by measuring how the Mn concentration in ZnSe varies with nanocrystal size and shape. Finally, we use our predictions to incorporate Mn into previously undopable CdSe nanocrystals. This success establishes that earlier difficulties with doping are not intrinsic, and suggests that a variety of doped nanocrystals--for applications from solar cells to spintronics--can be anticipated.

The critical role that dopants play in semiconductor devices has stimulated research on the properties and the potential applications of semiconductor nanocrystals, or colloidal quantum dots, doped with intentional impurities. We review advances in the chemical synthesis of doped nanocrystals, in the theoretical understanding of the fundamental mechanisms that control doping, and in the creation of highly conducting nanocrystalline films. Because impurities can be used to alter the properties of nanoscale materials in desirable and controllable ways, doped nanocrystals can address key problems in applications from solar cells to bioimaging.

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.

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We explore how the size and shape of the microscopic confinement potential affects the nonradiative Auger decay rate of confined carriers. Calculations conducted in the two-band, effective mass Kane model unambiguously show that smoothing out the confinement potential could reduce the rate by more than 3 orders of magnitude relative to the rate in structures with abruptly terminating boundaries. As the confinement potential width is increased, the calculated rate decreases overall, exhibiting very deep minima at regular widths. Such minima suggest that nanocrystals of "magic sizes" can exist for which nonradiative Auger processes are strongly suppressed.

The photoluminescence from a variety of individual molecules and nanometre-sized crystallites is defined by large intensity fluctuations, known as 'blinking', whereby their photoluminescence turns 'on' and 'off' intermittently, even under continuous photoexcitation. For semiconductor nanocrystals, it was originally proposed that these 'off' periods corresponded to a nanocrystal with an extra charge. A charged nanocrystal could have its photoluminescence temporarily quenched owing to the high efficiency of non-radiative (for example, Auger) recombination processes between the extra charge and a subsequently excited electron-hole pair; photoluminescence would resume only after the nanocrystal becomes neutralized again. Despite over a decade of research, completely non-blinking nanocrystals have not been synthesized and an understanding of the blinking phenomenon remains elusive. Here we report ternary core/shell CdZnSe/ZnSe semiconductor nanocrystals that individually exhibit continuous, non-blinking photoluminescence. Unexpectedly, these nanocrystals strongly photoluminesce despite being charged, as indicated by a multi-peaked photoluminescence spectral shape and short lifetime. To model the unusual photoluminescence properties of the CdZnSe/ZnSe nanocrystals, we softened the abrupt confinement potential of a typical core/shell nanocrystal, suggesting that the structure is a radially graded alloy of CdZnSe into ZnSe. As photoluminescence blinking severely limits the usefulness of nanocrystals in applications requiring a continuous output of single photons, these non-blinking nanocrystals may enable substantial advances in fields ranging from single-molecule biological labelling to low-threshold lasers.