We study the electronic properties of spherical quantum dot quantum well nanocrystals within a symmetry-based tight-binding model. In particular, the influence of a concentric monolayer of HgS embedded in a spherical CdS nanocrystal of diameter 52.7 A is analyzed as a function of its distance from the center. The electron and hole states around the energy gap show a strong localization in the HgS well and the neighboring inner (core) interface region. Important effects on the optical properties such as the absorption gap and the fine structure of the exciton spectrum are also reported.
The blinking dynamics of colloidal core-shell CdSe/CdS dot-in-rods is studied in detail at the single particle level. Analyzing the autocorrelation function of the fluorescence intensity, we demonstrate that these nanoemitters are characterized by a short value of the mean duration of bright periods (ten to a few hundreds of microseconds). The comparison of the results obtained for samples with different geometries shows that not only the shell thickness is crucial but also the shape of the dot- in-rods. Increasing the shell aspect ratio results in shorter bright periods suggesting that surface traps impact the stability of the fluorescence intensity.
Using a combination of continuous wave and time-resolved spectroscopy, we study the effects of interfacial conditions on the radiative lifetimes and photoluminescence intensities of colloidal CdTe/CdS quantum dots (QDs) embedded in a three-dimensional nanostructured silicon (NSi) matrix. The NSi matrix was thermally oxidized under different conditions to change the interfacial oxide thickness. QDs embedded in a NSi matrix with ~0.5 nm of interfacial oxide exhibited reduced photoluminescence intensity and nearly five times shorter radiative lifetimes (~16 ns) compared to QDs immobilized within completely oxidized, nanostructured silica (NSiO2) frameworks (~78 ns). Optical absorption by the sub-nm oxidized NSi matrix partially lowers QD emission intensities while non-radiative carrier recombination and phonon assisted transitions influenced by defect sites within the oxide and NSi are believed to be the primary factors limiting the QD exciton lifetimes in the heterostructures.
Colloidal quantum dots (cQDs) are now a mature nanomaterial with optical properties customizable through varying size and composition. However, their use in optical devices is limited as they are not widely available in convenient forms such as optical fibers. With advances in polymerization methods incorporating nanocrystals, nanocomposite materials suitable for processing into high quality hybrid active fibers can be achieved. We demonstrate a plastic optical fiber fabrication method which ensures homogeneous dispersion of cQDs within a polymer core matrix. Loading concentrations between 10$^{11}$-10$^{13}$ CdSe/CdS cQDs per cm$^{3}$ in polystyrene were electronically imaged, confirming only sporadic sub-wavelength aggregates. Rayleigh scattering losses are therefore dominant at energies below the semiconductors band gap, but are overtaken by a sharp CdS-related absorption onset around 525 nm facilitating cQD excitation. The redshifted photoluminescence emission is then minimally reabsorbed along the fiber with a spectrum barely affected by the polymerization and a quantum yield staying at $sim$65$%$ of its initial value. The latter, along with the glass transition temperature and refractive index, is independent of the cQD concentration hence yielding a proportionally increasing light output. Our cQD-doped fibers are photostable to within 5$%$ over days showing great promise for functional material applications.
Exciton spin dynamics in quasi-spherical CdS quantum dots is studied in detail experimentally and theoretically. Exciton states are calculated using the 6-band k.p Hamiltonian. It is shown that for various sets of Luttinger parameters, when the wurtzite lattice crystal field splitting and Coulomb interaction between the electron-hole pair are taken into account exactly, both the electron and hole wavefunction in the lowest exciton state are of S-type. This rules out the spatial-symmetry-induced origin of the dark exciton in CdS quantum dots. The exciton bleaching dynamics is studied using time- and polarization-resolved transient absorption technique of ultrafast laser spectroscopy. Several samples with a different mean size of CdS quantum dots in different glass matrices were investigated. This enabled the separation of effects that are typical for one particular sample from those that are general for this type of material. The experimentally determined dependence of the electron spin relaxation rate on the radius of quantum dots agrees well with that computed theoretically.
We investigate the influence of X-ray and gamma-ray irradiation on the photophysical properties of sub-monolayer CdTe/CdS quantum dots (QDs) immobilized in porous silica (PSiO2) scaffolds. The highly luminescent QD-PSiO2 thin films allow for straightforward monitoring of the optical properties of the QDs through continuous wave and time-resolved photoluminescence spectroscopy. The PSiO2 host matrix itself does not modify the QD properties. X-ray irradiation of the QD-PSiO2 films in air leads to an exponential decrease in QD emission intensity, an exponential blue-shift in peak emission energy, and substantially faster exciton decay rates with increasing exposure doses from 2.2 Mrad(SiO2) to 6.6 Mrad(SiO2). Gamma-ray irradiation of a QD-PSiO2 thin film at a total exposure dose of 700 krad(SiO2) in a nitrogen environment results in over 80% QD photodarkening but no concurrent blue-shift in peak emission energy due to a lack of photo-oxidative effects. Near-complete and partial reversal of irradiation-induced photodarkening was demonstrated on X-ray and gamma-ray irradiated samples, respectively, through the use of a surface re-passivating solution, suggesting that there are different contributing mechanisms responsible for photodarkening under different irradiation energies. This work contributes to improving the reliability and robustness of QD based heterogeneous devices that are exposed to high risk, high energy environments with the possibility of also developing QD-based large area, low-cost, re-useable, and flexible optical dosimeters.