Spin-polarizable excitonic luminescence in colloidal Mn2+-doped CdSe quantum dots

The photoluminescence of colloidal Mn2+-doped CdSe nanocrystals has been studied as a function of nanocrystal diameter. These nanocrystals are shown to be unique among colloidal doped semiconductor nanocrystals reported to date in that quantum confinement allows tuning of the CdSe bandgap energy across the Mn2+ excited-state energies. At small diameters, the nanocrystal photoluminescence is dominated by Mn 2+ emission. At large diameters, CdSe excitonic photoluminescence dominates. The latter scenario has allowed spin-polarized excitonic photoluminescence to be observed in colloidal doped semiconductor nanocrystals for the first time.     

Direct Observation of sp-d exchange interactions in colloidal Mn2+- and Co2+-doped CdSe quantum dots

The defining attribute of a diluted magnetic semiconductor (DMS) is the existence of dopant-carrier magnetic exchange interactions. In this letter, we report the first direct observation of such exchange interactions in colloidal doped CdSe nanocrystals. Doped CdSe quantum dots were synthesized by thermal decomposition of (Me4N)2[Cd4(SePh)10] in the presence of TMCl2 (TM2+ = Mn2+ or Co2+) in hexadecylamine and were characterized by several analytical and spectroscopic techniques. Using magnetic circular dichroism spectroscopy, successful doping and the existence of giant excitonic Zeeman splittings in both Mn2+- and Co2+-doped wurtzite CdSe quantum dots are demonstrated unambiguously.     

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.     

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.     

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.     

Site-selective spectroscopy in Sm(3+)-doped sol-gel-derived nano-glass-ceramics containing SnO(2) quantum dots

Nano-glass-ceramics of composition 95SiO(2)-5SnO(2) doped with 0.4 Sm(3+) (mol%) were synthesized by the thermal treatment of precursor sol-gel glasses. Structural and luminescence measurements were carried out. The precipitated SnO(2) nanocrystals in the glass matrix constitute a wide bandgap quantum-dot system with size comparable to the bulk exciton Bohr radius. A site-selective excitation, by energy transfer from the semiconductor host, reveals that a fraction of the Sm(3+) ions are incorporated in the SnO(2) nanocrystals, whereas the rest remains in the silica glassy phase. An evolution in the Sm(3+) emission spectra has been observed when the SnO(2) nanocrystals are excited with different UV wavelengths, which has been ascribed to selective excitation of nanocrystal sets with predetermined size.     

Photoluminescence of colloidal CdSe/ZnS quantum dots under oxygen atmosphere

The effects of oxygen versus vacuum ambients on colloidal CdSe/ZnS quantum dots (QDs) were studied using both continuous and time-resolved photoluminescence (PL) measurements. The PL intensities were found to be an order of magnitude higher in an oxygen atmosphere, which is explained by the passivation of surface defects by oxygen absorption. The decay of PL intensities can be best fitted by a biexponential function with lifetimes of approximately 1 ns for the fast decay and approximately 10 ns for the slow decay. Based on the emission-energy dependence of carrier lifetimes and of the amplitude ratio of the fast-decay component to the slow-decay component, we suggest that the fast and slow PL decay of colloidal CdSe/ZnS QDs is caused by the recombination of delocalized carriers in the internal core states and the localized carriers in the surface states, respectively.     

Large blue shift of the biexciton state in tellurium doped CdSe colloidal quantum dots

The exciton-exciton interaction energy of tellurium doped CdSe colloidal quantum dots is experimentally investigated. The dots exhibit a strong Coulomb repulsion between the two excitons, which results in a huge measured biexciton blue shift of up to 300 meV. Such a strong Coulomb repulsion implies a very narrow hole wave function localized around the defect, which is manifested by a large Stokes shift. Moreover, we show that the biexciton blue shift increases linearly with the Stokes shift. This result is highly relevant for the use of colloidal QDs as optical gain media, where a large biexciton blue shift is required to obtain gain in the single exciton regime.     

Amphoteric CdSe nanocrystalline quantum dots

The nanocrystal quantum dot (NQD) charge states strongly influence their electrical transport properties in photovoltaic and electroluminescent devices, optical gains in NQD lasers, and the stability of the dots in thin films. We report a unique electrostatic nature of CdSe NQDs, studied by electrophoretic methods. When we submerged a pair of metal electrodes, in a parallel plate capacitor configuration, into a dilute solution of CdSe NQDs in hexane, and applied a DC voltage across the pair, thin films of CdSe NQDs were deposited on both the positive and the negative electrodes. Extensive characterizations including scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) and Raman studies revealed that the films on both the positive and the negative electrodes were identical in every respect, clearly indicating that: (1)?a fraction (<1%) of the CdSe NQDs in free form in hexane solution are charged and, more importantly, (2)?there are equal numbers of positive and negative CdSe NQDs in the hexane solution. Experiments also show that the number of deposited dots is at least an order of magnitude higher than the number of initially charged dots, indicating regeneration. We used simple thermodynamics to explain such amphoteric nature and the charging/regeneration of the CdSe NQDs.     

Exciton dephasing time in CuBr quantum dots

We perform degenerate four-wave mixing on CuBr quantum dot samples on a femtosecond time scale. Due to inhomogeneous broadening, we observe a so called photon-echo signal. The signal dynamics measured at different pump intensities provide information on the dephasing time. We study this dephasing time at 5 K as a function of the excitation wavelength. We also determine the homogeneous absorption linewidth by spectral hole burning measurements, in the same sample, at 5 K, using a nanosecond dye laser excitation. This is an alternative indirect method to determine dephasing times and we can compare both results. We then conclude on the difficulties of measuring dephasing times in confined systems by the latter method.     

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.     

Effect of oxidation induced surface state formation on the properties of colloidal CdSe quantum dots

This article addresses on the issue of oxidation on the organically capped CdSe nanoparticles. The surface states properties of the nanoparticles were monitored as a function of time during the natural exposure to oxygen and light, to determine the long term stability of the CdSe quantum dots. CdSe nanoparticles were chemically prepared using three different compositional regimes, viz., Cd rich, Se rich, and stoichiometric and were of different sizes in the range of 5-7 nm. The optical and the structural properties in the three cases were significantly different when the nanoparticles were subjected to natural oxidation. The CdSe nanoparticles were probed using Ar+ ion sputtering used in conjunction with X-Ray Photoelectron Spectroscopy for structural analysis, where as the optical studies were done using UV-VIS and the Photoluminescent measurements. The results showed a blue shift and a considerable decrease in the intensity associated to surface states (lambda approximately 600-700 nm) in case of Se rich case, no shift in stoichiometric CdSe suggesting that its stable against oxidation, and a red shift in PL position in Cd rich regime. The Stoke's shift observed in the nonstoichiometric cases can be associated with the quantum confinement and the stress/strain effects. The result demonstrate the role of Cd/Se stoichiometry in tuning the surface states for tailoring the desired optical properties.     

Extracellular biosynthesis of biocompatible CdSe quantum dots

An extracellular biosynthesis method has been developed to prepare cadmium selenide (CdSe) quantum dots (QDs) with strong fluorescence emission by incubating cheap Cd and Se inorganic salts with Escherichia coli (E.coli) bacteria. Ultraviolet–visible absorption spectra, photoluminescence (PL) spectra, and high‐resolution transmission electron microscopy analysis showed that the biosynthesised CdSe QDs have an average size of 3.1 nm, the excellent optical properties with fluorescence emission around 494 nm, and the good crystallinity. It was found that addition of 80 mg of mercaptosuccinic acid resulted in the formation of CdSe QDs with highest PL intensity. Furthermore, Fourier‐transform infrared spectra of as‐synthesised CdSe QDs confirmed the presence of a surface protein capping layer. The biosynthesised CdSe QDs were incorporated into the yeast cells as illustrated by laser confocal scanning microscopy images, showing a great potential in bio‐imaging and bio‐labelling application.Inspec keywords: microorganisms, molecular biophysics, fluorescence, visible spectra, nanofabrication, nanobiotechnology, proteins, cellular biophysics, nanostructured materials, wide band gap semiconductors, cadmium compounds, semiconductor quantum dots, II‐VI semiconductors, transmission electron microscopy, photoluminescence, optical microscopy, ultraviolet spectra, Fourier transform infrared spectra, biological techniques, semiconductor growthOther keywords: biocompatible CdSe quantum dots, extracellular biosynthesis method, cadmium selenide quantum dots, high‐resolution transmission electron microscopy analysis, biosynthesised CdSe QDs, Fourier‐transform infrared spectra, Escherichia coli, ultraviolet‐visible absorption spectra, PL intensity, fluorescence emission, photoluminescence spectra, optical properties, surface protein capping layer, laser confocal scanning microscopy images, bioimaging, biolabelling application, yeast cells, f mercaptosuccinic acid, CdSe     

Ultrafast spin dynamics in colloidal ZnO quantum dots

Time-resolved Faraday rotation measurements in the ultraviolet have been performed to reveal the ultrafast spin dynamics of electrons in colloidal ZnO quantum dots. Oscillating Faraday rotation signals are detected at frequencies corresponding to an effective g factor of g = 1.96. Biexponential oscillation decay is observed that is due to (i) rapid depopulation of the fundamental exciton (tau = 250 ps) and (ii) slow electron spin dephasing ( T 2 = 1.2 ns) within a metastable state formed by hole-trapping at the quantum dot surface.     

Recombination dynamics in CdTe/CdSe type-II quantum dots

Recombination dynamics in CdTe/CdSe core-shell type-II quantum dots (QDs) has been investigated by time-resolved photoluminescence (PL) spectroscopy. A very long PL decay time of several hundred nanoseconds has been found at low temperature, which can be rationalized by the spatially separated electrons and holes occurring in a type-II heterostructure. For the temperature dependence of the radiative lifetime, the linewidth and the peak energy of PL spectra show that the recombination of carriers is dominated by delocalized excitons at temperatures below 150?K, while the mixture of delocalized excitons, electrons and holes overwhelms the process at higher temperature. The binding energy of delocalized excitons obtained from the temperature dependence of the non-radiative lifetime is consistent with the theoretical value. The energy dependence of lifetime measurements reveals a third power relationship between the radiative lifetime and the radius of QDs, the light of which can be shed by the quantum confinement effect. In addition, the radiative decay rate is found to be proportional to the square root of excitation power, arising from the change of wavefunction overlap of electrons and holes due to the band bending effect, which is an inherent character of a type-II band alignment.     

Multi-wavelength intermittent photoluminescence of single CdSe quantum dots

A single chromophore detection using video-microscopy is one of the latest methodologies to reveal unique characteristics, which could not be obtained from ensemble measurements. Among many kinds of subjects, dynamic optical properties observed in colloidal semiconductor nanoparticles are attractive and important not only for the basis of photo-physics but also for application studies, e.g. biological labeling, electronic devices. In this study, fluorescence video-microscopy was performed on cadmium selenide (CdSe) quantum dots (QDs) spin-coated on a glass substrate. From single CdSe QDs detection, emissions at wavelengths separated over 60 nm were observed for the first time. This spectral feature was attributed to the existence of double-emissive relaxation processes in CdSe QDs. Photoluminescence intermittency was also observed both from relaxation processes. Fluorescence video-microscopy, which was advanced in biology, can be applicable for the real-time monitoring of dynamic properties in semiconductor photo-physics.     

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.     

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.