Towards non-blinking colloidal quantum dots

At a single-molecule level, fluorophore emission intensity fluctuates between bright and dark states. These fluctuations, known as blinking, limit the use of fluorophores in single-molecule experiments. The dark-state duration shows a universal heavy-tailed power-law distribution characterized by the occurrence of long non-emissive periods. Here we have synthesized novel CdSe-CdS core-shell quantum dots with thick crystalline shells, 68% of which do not blink when observed individually at 33 Hz for 5 min. We have established a direct correlation between shell thickness and blinking occurrences. Importantly, the statistics of dark periods that appear at high acquisition rates (1 kHz) are not heavy tailed, in striking contrast with previous observations. Blinking statistics are thus not as universal as thought so far. We anticipate that our results will help to better understand the physico-chemistry of single-fluorophore emission and rationalize the design of other fluorophores that do not blink.     

Ultrafast dynamics of excitons in semiconductor quantum dots on a plasmonically active nano-structured silver film

The excited state dynamics of core-shell type semiconductor quantum dots (QDs) of various sizes in close contact with a plasmonically active silver thin film has been demonstrated by using picosecond resolved fluorescence spectroscopy. The non-radiative energy transfer from the QDs to the metal surface is found to be of F?rster resonance energy transfer (FRET) type rather than the widely expected nano-surface energy transfer (NSET) type. The slower rate of energy transfer processes compared to that of the electron transfer from the excited QDs to an organic molecule benzoquinone reveals an insignificant possibility of charge migration from the QDs to the metallic film.     

Optical properties of HgTe colloidal quantum dots

Room temperature photodetection with HgTe colloidal quantum films is reported between 2 and 5 μm for particles of sizes between ~5 and ~12 nm diameter, and photodetection extends to 7 μm at 80 K. The size-tuning of the absorption of HgTe colloidal quantum dots, their optical cross section and the infrared absorption depth of films are measured. The tuning with radius is empirically given by [see formula in text] where R is in nm. The optical cross section of the colloidal dots at 415 nm is approximately proportional to their volume and given by σ(Hg)(415) = 2.6 ± 0.4 10(-17) cm(2)/mercury atom. The size-dependent optical cross section at the band edge ~1.5 10(-15) cm(2) is consistent with the expected oscillator strength of the quantum dots. The absorption depth of HgTe colloidal dot films is short, about 1-2 μm, which is an advantage for thin film devices. These properties agree rather well with the expectation from the k · p model. HgTe colloidal quantum dot thin films show a strong tuning with temperature with a large positive thermal shift between 0.4 and 0.2 meV K(-1), decreasing with decreasing size within the size range studied and this is attributed primarily to electron-phonon effects.     

Slow hot-carrier relaxation in colloidal graphene quantum dots

Reducing hot-carrier relaxation rates is of great significance in overcoming energy loss that fundamentally limits the efficiency of solar energy utilization. Semiconductor quantum dots are expected to have much slower carrier cooling because the spacing between their discrete electronic levels is much larger than phonon energy. However, the slower carrier cooling is difficult to observe due to the existence of many competing relaxation pathways. Here we show that carrier cooling in colloidal graphene quantum dots can be 2 orders of magnitude slower than in bulk materials, which could enable harvesting of hot charge carriers to improve the efficiency of solar energy conversion.     

Ultrafast near-field spectroscopy of single semiconductor quantum dots

Excitonic and spin excitations of single semiconductor quantum dots (QDs) currently attract attention as possible candidates for solid-state-based implementations of quantum logic devices. Due to their rather short decoherence times in the picosecond to nanosecond range, such implementations rely on using ultrafast optical pulses to probe and control coherent polarizations. We combine ultrafast spectroscopy and near-field microscopy to probe the nonlinear optical response of a single QD on a femtosecond time-scale. Transient reflectivity spectra show pronounced oscillations around the QD exciton line. These oscillations reflect phase-disturbing Coulomb interactions between the excitonic QD polarization and continuum excitations. The results show that although semiconductor QDs resemble in many respects atomic systems, Coulomb many-body interactions can contribute significantly to their optical nonlinearities on ultrashort time-scales.     

Low temperature synthesis of colloidal CdSe quantum dots

In this study, the CdSe nanocrystals were prepared in phenyl ether and octyl amine to investigate the variations of their size, bandgap energy, and photoluminescence with growth time and temperature. The sizes of the CdSe nanocrystals were measured using High Resolution Transmission Electron Microscopy (HRTEM), and found to be nearly monodisperse for relatively low growth temperature, 130 degrees C. Their optic properties were characterized by photoluminescence measurements, which showed that the colors of the nanocrystals could be controlled. The bandgap energies of the nanocrystals were calculated theoretically and found to be in accord with quantum confinement theory. This synthetic method requires only a cheap solvent and offers good reproducibility at a lower price.     

Coherent spin transport through dynamic quantum dots

Spin transport and manipulation in semiconductors have been studied intensively with the ultimate goal of realizing spintronic devices. Previous work in GaAs has focused on controlling the carrier density, crystallographic orientation and dimensionality to limit the electron spin decoherence and allow transport over long distances. Here, we introduce a new method for the coherent transport of spin-polarized electronic wave packets using dynamic quantum dots (DQDs) created by the piezoelectric field of coherent acoustic phonons. Photogenerated spin carriers transported by the DQDs in undoped GaAs (001) quantum wells exhibit a spin coherence length exceeding 100 microm, which is attributed to the simultaneous control of the carrier density and the dimensionality by the DQDs during transport. In the absence of an applied magnetic field, we observe the precession of the electron spin induced by the internal magnetic field associated with the spin splitting of the conduction band (Dresselhaus term). The coherent manipulation of the precession frequency is also achieved by applying an external magnetic field.     

Tunable optical properties of colloidal quantum dots in electrolytic environments

The absorption spectra of colloidal cadmium sulfide quantum dots in electrolytic solutions are found to manifest a shift in the absorption threshold as the concentration of the electrolyte is varied. These results are consistent with a shift in the absorption threshold that would be caused by electrolytic screening of the field caused by the intrinsic spontaneous polarisation of these würtzite structured quantum dots. These electrolyte-dependent absorption properties provide a potential means of gaining insights on the variable extracellular and intracellular electrolytic concentrations that are present in biological systems.     

Infrared photodiode based on colloidal PbSe nanocrystal quantum dots

We report in this paper our studies on the photoconductivity and photovoltaic effects of colloidal PbSe nanocrystal quantum dots (NQDs) which were embedded in conductive polymer matrices to form hybrid polymer/NQD infrared photodiodes. The generation of photocarriers in PbSe NQDs and their transport in NQD-polymer composites were described by a simplified band diagram picture of the device. Both photocurrent and photovoltage outputs were measured from the NQD-incorporated photodiode upon the illumination of near-infrared (NIR) light, whereas the net polymer-based devices do not exhibit any photoresponsivity. The intensity dependence of the photocurrent indicates the pseudomonomolecular recombination kinetics in the NQD-polymer composite. The measured photocurrent spectrum is consistent with the absorption characteristic of PbSe NQDs. Further enhancement of the photodiode efficiency can be achieved by engineering the nanocrystal surface to reduce the potential barriers due to the ligant capping molecules.     

Alignment of colloidal graphene quantum dots on polar surfaces

Controlling the orientation of nanostructures with anisotropic shapes is essential for taking advantage of their anisotropic electrical, optical, and transport properties in electro-optical devices. For large-area alignment of nanocrystals, so far orientations are mostly induced and controlled by external physical parameters, such as applied fields or changes in concentration. Herein we report on assemblies of colloidal graphene quantum dots, a new type of disk-shaped nanostructures, on polar surfaces and the control of their orientations. We show that the orientations of the graphene quantum dots can be determined, either in- or out-of-plane with the substrate, by chemical functionalization that introduces orientation-dependent interactions between the quantum dots and the surfaces.     

A perspective on functionalizing colloidal quantum dots with DNA

This perspective provides an overview of the techniques that have been developed for the conjugation of DNA to colloidal quantum dots (QDs), or semiconductor nanocrystals. Methods described include: ligand exchange at the QD surface, covalent conjugation of DNA to the QD surface ligands, and one-step DNA functionalization on core QDs or during core/shell QD synthesis in aqueous solution, with an emphasis on the most recent progress in our lab. We will also discuss emerging trends in DNA-functionalized QDs for potential applications.      

Emission properties of colloidal quantum dots on polyelectrolyte multilayers

We present steady state and time-resolved photoluminescence (PL) characteristics of differently charged CdTe quantum dots (QDs) adsorbed onto a polyelectrolyte (PE) multilayer. The PE multilayer is built up using a layer-by-layer assembly technique. We find that the diffusion of the QDs into the PE multilayer is an important factor in the case of 3-mercapto-1, 2-propanediol stabilized QDs (neutral surface charge), resulting in a ～31-fold enhancement in PL intensity accompanied by a blue shift in the PL spectra and an increase in decay lifetime from 3.74?ns to a maximum of 11.65?ns. These modified emission properties are attributed to the enhanced surface related emission resulting from the interaction of the QD's surface with the PE. We find that diffusion does not occur for thioglycolic acid (TGA) stabilized QDs (negative surface charge) or 2-mercaptoethylamine stabilized QDs (positive surface charge), indicating localization of the QDs on top of the PE multilayer. However, the PL lifetime of the TGA stabilized QDs decreases from 9.58 to 5.78?ns with increasing PE multilayer thickness. This provides evidence for increased intrinsic exciton recombination relative to surface related emission, which results in an overall reduction in the average lifetime. Our studies indicate the importance of the QD surface charge in determining the interaction with the PE multilayers and the subsequent modification of the QD emission properties.     

Shell distribution on colloidal CdSe/ZnS quantum dots

Scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) was used to determine the chemical distribution of semiconductor shell material around colloidal core-shell CdSe/ZnS quantum dots (QDs). EELS signals from positions around the QD indicate a well-defined shell of ZnS surrounding the CdSe core, but the distribution of the shell material is highly anisotropic. This nonuniformity may reflect the differences in chemical activity of the crystal faces of the core QD and implies a nonoptimal QD surface passivation.     

Sensitization of ZnO nanorods with CdSe quantum dots

We have optimized the low-temperature growth of aligned arrays of zinc oxide nanorods of controlled length and diameter on conductive substrates. Varying the solution concentration and growth time, we were able to tune the nanorod diameter and length in the ranges 40–600 nm and 0.5–15 μm, respectively. The grown zinc oxide nanorods were photosensitized with CdSe quantum dots (QDs) in an oleic shell, which was replaced by pyridine. We studied the optical and transport properties of the ZnO nanorod arrays, with and without CdSe QDs on their surface. The current-voltage characteristics of the ZnO nanorod arrays with CdSe QDs are significantly influenced by illumination with light at a wavelength under the absorption band of the QDs, which points to effective interaction between the QDs and ZnO matrix.     

Ultrafast carrier dynamics of near-band-edge emission in single-crystal ZnO nanorods

We report on rational synthesis and optical characteristics of highly crystallined ZnO nanorods which were grown by a facile chemical vapor transport method. Temperature-dependent photoluminescence spectra of as-fabricated ZnO nanorods are dominated by near-band-edge emission with a characteristic fine structure due to high crystallinity. Furthermore, the recombination emission involving carrier dynamics of near-band-edge emission in ZnO nanorods was systematically investigated by temperature-dependent time-resolved photoluminescence spectroscopy. Recombination peaks pertaining to the exciton emissions are monitored and resolved in both temporal and spatial regimes.     

Dipolar structures in colloidal dispersions of PbSe and CdSe quantum dots

We show by cryogenic transmission electron microscopy that PbSe and CdSe nanocrystals of various shapes in a liquid colloidal dispersion self-assemble into equilibrium structures that have a pronounced dipolar character, to an extent that depends on particle concentration and size. Analyzing the cluster-size distributions with a one-dimensional (1D) aggregation model yields a dipolar pair attraction of 8-10 kBT at room temperature. This accounts for the long-range alignment of the crystal planes of individual nanocrystals in self-assembled superstructures and for anisotropic nanostructures grown via oriented attachment.