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Crossover from 'mesoscopic' to 'universal' phase for electron transmission in quantum dots.

The measurement of phase in coherent electron systems--that is, 'mesoscopic' systems such as quantum dots--can yield information about fundamental transport properties that is not readily apparent from conductance measurements. Phase measurements on relatively large quantum dots recently revealed that the phase evolution for electrons traversing the dots exhibits a 'universal' behaviour, independent of dot size, shape, and electron occupancy. Specifically, for quantum dots in the Coulomb blockade regime, the transmission phase increases monotonically by pi throughout each conductance peak; in the conductance valleys, the phase returns sharply to its starting value. The expected mesoscopic features in the phase evolution--related to the dot's shape, spin degeneracy or to exchange effects--have not been observed, and there is at present no satisfactory explanation for the observed universality in phase behaviour. Here we report the results of phase measurements on a series of small quantum dots, having occupancies of between only 1-20 electrons, where the phase behaviour for electron transmission should in principle be easier to interpret. In contrast to the universal behaviour observed thus far only in the larger dots, we see clear mesoscopic features in the phase measurements when the dot occupancy is less than approximately 10 electrons. As the occupancy increases, the manner of phase evolution changes and universal behaviour is recovered for some 14 electrons or more. The identification of a transition from the expected mesoscopic behaviour to universal phase evolution should help to direct and constrain theoretical models for the latter.

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Dynamics of coherent and incoherent spin polarizations in ensembles of quantum dots.

The temperature dependence of spin coherence in InGaAs quantum dots is obtained from quantum beats observed in polarization-resolved pump-probe experiments. Within the same sample we clearly distinguish between coherent spin dynamics leading to quantum beats and incoherent long-lived spin-memory effects. Analysis of the coherent data using a theoretical model reveals approximately 10 times greater stability of the spin coherence at high temperature compared to that found previously for exciton states in four-wave-mixing experiments by Borri et al. [Phys. Rev. Lett. 87, 157401 (2001)]]. The data on incoherent polarization reveal a new form of spin memory based on charged quantum dots.

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Photophysical properties of biologically compatible CdSe quantum dot structures.

The photophysical properties of CdSe and ZnS(CdSe) semiconductor quantum dots in nonpolar and aqueous solutions were examined with steady-state (absorption and emission) and time-resolved (time-correlated single-photon-counting) spectroscopy. The CdSe structures were prepared from a single CdSe synthesis, a portion of which were ZnS-capped, thus any differences observed in the spectral behavior between the two preparations were due to changes in the molecular shell. Quantum dots in nonpolar solvents were surrounded with a trioctylphosphine oxide (TOPO) coating from the initial synthesis solution. ZnS-capped CdSe were initially brighter than bare uncapped CdSe and had overall faster emission decays. The dynamics did not vary when the solvent was changed from hexane to dichloromethane; however, replacement of the TOPO cap by pyridine affected CdSe but not ZnS(CdSe). CdSe was then solubilized in water with mercapto-acetic acid or dihydrolipoic acid, whereas ZnS(CdSe) could be solubilized only with dihydrolipoic acid. Both solubilization agents quenched the nanocrystal emission, though with CdSe the quenching was nearly complete. Additional quenching of the remaining emission was observed when the redox-active molecule adenine was conjugated to the water-soluble CdSe but was not seen with ZnS(CdSe). The emission of aqueous CdSe could be enhanced under prolonged exposure to room light and resulted in a substantial increase of the emission lifetimes; however, the enhancement occurred concurrently with precipitation of the nanocrystals, which was possibly caused by photocatalytic destruction of the mercaptoacetic acid coating. These results are the first presented on aqueous CdSe quantum dot structures and are presented in the context of designing better, more stable biological probes.

Cadmium Compounds↗

In vivo optical imaging using quantum dots for the management of brain tumors.

The surgical management of brain tumors requires the precise localization of tumor tissues within normal brain parenchyma in order to achieve accurate diagnostic biopsy and complete surgical resection. Quantum dots are optical semiconductor nanocrystals that exhibit stable, bright fluorescence. The intravenous injection of quantum dots is accompanied by reticuloendothelial system and macrophage sequestration. Macrophages infiltrate brain tumors and phagocytize intravenously injected quantum dots, optically labeling the tumors. Macrophage-mediated delivery of quantum dots to brain tumors may represent a novel technique to label tumors preoperatively. Quantum dots within tumors may be detected with optical imaging and optical spectroscopy tools, providing the surgeon with real-time optical feedback during the resection and biopsy of brain tumors.

Animals↗

Exciton Rabi oscillation in a single quantum dot.

A spectroscopic method, which enables characterization of a single isolated quantum dot and a quantum wave function interferometry, is applied to an exciton discrete excited state in an InGaAs quantum dot. Long coherence of zero-dimensional excitonic states made possible the observation of coherent population flopping in a 0D excitonic two-level system in a time-domain interferometric measurement. Corresponding energy splitting is also manifested in an energy-domain measurement.

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Tunable Fermi-edge resonance in an open quantum dot.

Resonant tunneling in an open mesoscopic quantum dot is proposed as a vehicle to realize a tunable Fermi-edge resonance with variable coupling strength. We solve the x-ray edge problem for a generic nonseparable scatterer and apply it to describe tunneling in a quantum dot. The tunneling current power law exponent is linked to the S matrix of the dot. The control of scattering by varying the dot shape and coupling to the leads allows us to explore a wide range of exponents. The sensitivity of mesoscopic coherence to the Wigner-Dyson ensemble symmetry is replicated in the Fermi-edge singularity.

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Finite-size effects in conductance measurements on quantum dots.

The observation of the Kondo effect in quantum dots has provided new opportunities to finally observe the controversial Kondo screening cloud. Here we study the conductance of a quantum dot embedded in a finite length quantum wire, predicting a change in behavior when the length of the wire is comparable to the size of the screening cloud.

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Excitation dynamics in a three-quantum dot system driven by optical near-field interaction: towards a nanometric photonic device.

Using density operator formalism, we discuss interdot excitation energy transfer dynamics driven by the optical near-field and phonon bath reservoir, as well as coherent excitation dynamics of a quantum dot system. As an effective interaction between quantum dots induced by the optical near-field, the projection operator method gives a renormalized dipole interaction, which is expressed as a sum of the Yukawa functions and is used as the optical near-field coupling of quantum dots. We examine one- and two-exciton dynamics of a three-quantum dot system suggesting a nanometric photonic switch, and numerically obtain a transfer time comparable with the recent experimental results for CuCl quantum dots.

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Quenching of semiconductor quantum dot photoluminescence by a pi-conjugated polymer.

In this communication we discuss the possibility of hole transfer between a photoexcited semiconductor quantum dot and a pi-conjugated polymer. This charge-transfer event will be investigated (exploited) on the basis of its implication toward a solar energy conversion scheme. Experimentally, we show that the steady-state photoluminescence (PL) of a solution of InP quantum dots is quenched by the introduction of solvated poly(3-hexylthiophene). Time-resolved PL experiments on these solutions are also presented. It was observed that the PL transients did not significantly change upon the addition of the conductive polymer. These new results indicate that said PL quenching is static in nature. This suggests that in solution, the quantum dot and the polymer exhibit a strong intermolecular interaction. As the two species encounter each other through diffusion, the polymer quenches the quantum dot photoluminescence without altering the population's PL lifetime. This new evidence suggests that the polymer and the quantum dot form a relatively stable complex.

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New synthetic routes for quantum dots.

Various methods for the synthesis of quantum dots of compound semiconductors are discussed. Emphasis is placed on methods involving the decomposition of chalcogenide-containing precursors in tri-n-octylphosphine oxide. The use of simple coordination complexes can avoid the use of pyrophoric precursors. Approaches based on melts or the use of imino-bisdichalcogeno-diphosphinates are also discussed. These routes may be suitable for the production of large quantities of quantum dots.

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Nonlinear optical approach to multiexciton relaxation dynamics in quantum dots.

Unlike the majority of molecular systems quantum dots can accommodate multiple excitations, which is a particularly important attribute for potential lasing applications. We demonstrate in this work the concept of using nth order nonlinear spectroscopies in the transient grating configuration as a means of selectively exciting (n-1)/2 excitons in a semiconductor and probing the subsequent relaxation dynamics. We report a direct observation of multiparticle dynamics on ultrashort time scales through comparison of third and fifth order experiments for CdSe colloidal quantum dots. Time constants associated with multiexciton recombination and depopulation dynamics are reported. Deviation from a Poisson model for the distribution of photoexcited excitons, biexcitons, and triexcitons is also discussed.

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Fine structure of highly charged excitons in semiconductor quantum dots.

An exciton in a symmetric semiconductor quantum dot has two possible states, one dark and one bright, split in energy by the electron-hole exchange interaction. We demonstrate that for a doubly charged exciton, there are also two states split by the electron-hole exchange, but both states are now bright. We also uncover a fine structure in the emission from the triply charged exciton. By measuring these splittings, and also those from the singly charged and doubly charged biexcitons, all on the same quantum dot, we show how the various electron-hole exchange energies can be measured without having to break the symmetry of the dot.

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Quantum dots are powerful multipurpose vital labeling agents in zebrafish embryos.

Recently, inorganic fluorescent contrast agents composed of semiconductor materials have been introduced to biological imaging approaches. These so-called quantum dots provide unique and promising properties unreached by organic fluorophores, but their use as contrast agents within live organisms has been limited, probably due in part to concerns about their in vivo tolerance. Using transparent zebrafish embryos, we challenged quantum dots with a series of intravital imaging problems. We show that quantum dots provide a high fluorescent yield within targeted tissues, possess immense photostability, can be targeted to specific subcellular compartments, remain within targeted cells as lineage tracers, are easily separable from conventional organic fluorescent dyes, and are fixable, allowing them to be used in combination with immunohistochemistry after live recordings. Thus, quantum dots combine the specific advantages of different organic fluorescent contrast agents and promise to become the first fluorophore feasible for long-lasting intravital time-lapse studies. Finally, we show by co-labeling blood vessels of the vasculature and major axon tracts of the nervous system that, for establishing these networks, the same guidance cues might be used in some body parts, whereas in others, both networks appear to develop independently from one another. Thus, the bright fluorescence of quantum dots will help to unravel many open questions in the fields of embryology, cell biology, as well as phenotyping and disease diagnosis.

Animals↗

A modeling and convolution method to measure compositional variations in strained alloy quantum dots.

We have developed a method to quantitatively measure the absolute composition of nanometer sized capped quantum dots in semiconductor alloys. The method uses spatially resolved electron energy-loss spectroscopy in a scanning transmission electron microscope to measure compositional profiles across the center of the quantum dot and the adjacent nanometer wide wetting layer. The measurements from the wetting layer are used to derive a spatial broadening function which includes the effects of probe size, instabilities and beam spreading in the sample. This broadening function is employed to simulate compositional profiles from the quantum dots. Information on the dimensions of dots is extracted from annular dark-field images. The method is applied to In(y)Ga(1-y)As (y = 0.5) quantum dots grown on a GaAs substrate. In this system, a simple truncated cone model is found to give an adequate description of the compositional variations across the dot. We find a substantial enrichment in In at the center of the dots, in agreement with theoretical predictions.

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Quantum dots as fluorescent labels for quantitative detection of Salmonella typhimurium in chicken carcass wash water.

Fluorescent semiconductor quantum dots have recently emerged as a novel and promising class of fluorescent labels for biological detection. In this study, quantum dots were used as fluorescent labels in immunoassays for quantitative detection of foodborne pathogenic bacteria. Salmonella Typhimurium cells were separated from chicken carcass wash water using anti-Salmonella antibody coated magnetic beads and reacted to secondary biotin-labeled anti-Salmonella antibody. Quantum dots coated with streptavidin were added to react with biotin on the secondary antibody. Measurement of the intensity of fluorescence produced by quantum dots provided a quantitative method for microbial detection. A linear relationship between Salmonella Typhimurium cell number (log N) in the samples of chicken carcass wash water and the fluorescence intensity (FI) was found for the cell numbers ranging from 10(3) to 10(7) CFU/ml. The regression model can be expressed as FI = 198.6 Log N - 639.03 with R2 = 0.96. The detection limit of this method was 10(3) CFU/ml.

Animals↗

Self-organized CdSSe quantum dots thin films.

Self-organized and strained CdSSe quantum dot (Q-dot) thin films have been grown on ITO-coated glass substrates by novel wet chemical route. The Q-dots are (002) oriented faceted pyramids with average particle size of 7.5 nm. The X-ray diffraction results reveal the formation of a solid solution of CdSSe. Atomic force microscopy is used to investigate the morphology of the nanocrystalline thin films. The energy dispersive X-ray analysis spectrum confirms the presence of Cd, S, and Se in the films. Optical absorption and photoluminescence spectra show the blue shift for quantum dot thin films.

Cadmium Compounds↗

Control of vertically coupled InGaAs/GaAs quantum dots with electric fields.

Controllable interactions that couple quantum dots are a key requirement in the search for scalable solid state implementations for quantum information technology. From optical studies of excitons and corresponding calculations, we demonstrate that an electric field on vertically coupled pairs of In(0.6)Ga(0.4)As/GaAs quantum dots controls the mixing of the exciton states on the two dots and also provides controllable coupling between carriers in the dots.

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Single-molecule measurements of gold-quenched quantum dots.

We report the study of the quenching of quantum dots (CdSe) by gold nanoparticles at the single-molecule level. Double-stranded DNA is used as a rigid spacer to tune the distance between the two nanoparticles. The width of the fluorescent intensity distribution, monitored at different interparticle distances, reflects both the nanoparticle heterogeneity and the fluorescence intermittency of the quantum dot. The fluorescence distribution emitted by single CdSe nanocrystals can easily be distinguished from the fluorescence of partially quenched CdSe. Our results show that the distance-dependence quenching is compatible with a Förster-type process.

Cadmium Compounds↗