The time dynamics of the photoexcited carriers and carrier-multiplication efficiencies in PbS quantum dots (QDs) are investigated. In particular, we report on the carrier dynamics, including carrier multiplication, as a function of QD size and compare them to the bulk value. We show that the intraband 1P→1S decay becomes faster for smaller QDs, in agreement with the absence of a phonon bottleneck. Furthermore, as the size of the QDs decreases, the energy threshold for carrier multiplication shifts from the bulk value to higher energies. However, the energy threshold shift is smaller than the band-gap shift and, therefore, for the smallest QDs, the threshold approaches 2.35 E g , which is close to the theoretical energy conservation limit of twice the band gap. We also show that the carrier-multiplication energy efficiency increases with decreasing QD size. By comparing to theoretical models, our results suggest that impact ionization is sufficient to explain carrier multiplication in QDs.

A chromophore in which zinc porphyrin donors are linked through their meso positions by ethynyl bridges to a bis(indolinylidenemethyl) squaraine core has been synthesized using Sonogashira coupling. The chromophore exhibits a two-photon absorption spectrum characterized by a peak cross section of 11,000 GM and, more unusually, also exhibits a large cross section of >780 GM over a photon-wavelength window 750 nm in width.

The two-photon absorption, 2PA, cross sections of PbS quantum dots, QDs, are theoretically and experimentally investigated and are shown to be enhanced with increasing quantum confinement. This is in contrast to our previous results for CdSe and CdTe QDs where the reduced density of states dominated and resulted in a decrease in 2PA with a decrease in QD size. Qualitatively this trend can be understood by the highly symmetric distribution of conduction and valence band states in PbS that results in an accumulation of allowed 2PA transitions in certain spectral regions. We also measure the frequency nondegenerate 2PA cross sections that are up to five times larger than for the degenerate case. We use a k·p four-band envelope function formalism to model the increasing trend of the two-photon cross sections due to quantum confinement and also due to resonance enhancement in the nondegenerate case.

The influence of quantum confinement on the one- and two-photon absorption spectra (1PA and 2PA) of PbS and PbSe semiconductor quantum dots (QDs) is investigated. The results show 2PA peaks at energies where only 1PA transitions are predicted and 1PA peaks where only 2PA transitions are predicted by the often used isotropic k x p four-band envelope function formalism. The first experimentally identified two-photon absorption peak coincides with the energy of the first one photon allowed transition. This first two-photon peak cannot be explained by band anisotropy, verifying that the inversion symmetry of the wave functions is broken and relaxation of the parity selection rules has to be taken into account to explain optical transitions in lead-salt QDs. Thus, while the band anisotropy of the bulk semiconductor plays a role in the absorption spectra, especially for the more anisotropic PbSe QDs, a complete model of the absorption spectra, for both 1PA and 2PA, must also include symmetry breaking of the quantum confined wave functions. These studies clarify the controversy of the origin of spectral features in lead-salt QDs.

Lead (II) oxide powder (PbO, 99.999%), Bis (trimethylsilyl) sulfide (TMS), Oleic acid (OA, technical grade 90%), 1-Octadecene (ODE, technical grade 90%), and anhydrous Toluene were purchased from Sigma-Aldrich. Distilled Acetone was purchased from Caledon Lab. Bistrimethylsilylselenide (TMSe>97%) was purchased from Gelest. ODE was degassed by pre-pumping at 80oC for 16 hours. QDs synthesis:The QDs were synthesized and purified using standard air-free techniques in two-neck flask equipped with magnetic stirrer, thermocouple, and heating mantle.Lead oleate stock solution (SS) used for PbS and PbSe synthesis was prepared by pumping the mixture of 4.0 mmol of PbO (0.9 g), 9.5mmol of OA (2.67 g) and 18.8 mmol of ODE (4.73 g) at 100oC for 16 hours. The sulfur or selenium precursors were prepared in a Nitrogen-filled Glove box. A mixture of 4.5 mL of SS and 15 mL of ODE was pre-pumped at 100 0 C for 30 min for each synthesis. The sulfur or selenium precursors were quickly injected at a certain temperature. Than the heater then was turned off without removing the heating mantel and the reaction flask was let to cool down slowly.

Electron beam and optical depth profiling of thick (5.5–64 μm) quasibulk n-type GaN samples, grown by hydride vapor-phase epitaxy, were carried out using electron beam induced current (EBIC), microphotoluminescence (PL), and transmission electron microscopy (TEM). The minority carrier diffusion length, L, was found to increase linearly from 0.25 μm, at a distance of about 5 μm from the GaN/sapphire interface, to 0.63 μm at the GaN surface, for a 36-μm-thick sample. The increase in L was accompanied by a corresponding increase in PL band-to-band radiative transition intensity as a function of distance from the GaN/sapphire interface. We attribute the latter changes in PL intensity and minority carrier diffusion length to a reduced carrier mobility and lifetime at the interface, due to scattering at threading dislocations. The results of EBIC and PL measurements are in good agreement with the values for dislocation density obtained using TEM.

The linear and nonlinear absorption properties of a squaraine-bridged porphyrin dimer (POR-SQU-POR) are investigated using femto-, pico-, and nanosecond pulses to understand intramolecular processes, obtain molecular optical parameters, and perform modeling of the excited-state dynamics. The optical behavior of POR-SQU-POR is compared with its separate porphyrin and squaraine constituent moieties. Linear spectroscopic studies include absorption, fluorescence, excitation and emission anisotropy, and quantum yield measurements. Nonlinear spectroscopic studies are performed across a wide range (approximately 150 fs, approximately 25 ps, and approximately 5 ns) of pulsewidths and include two-photon absorption (2PA), single and double pump-probe, and Z-scan measurements with detailed analysis of excited-state absorption induced by both one- and two-photon absorption processes. The 2PA from the constituent moieties shows relatively small 2PA cross sections; below 10 GM (1 GM = 1 x 10(-50) cm4 s/photon) for the porphyrin constituent and below 100 GM for the squaraine constituent except near their one-photon resonances. In stark contrast, the composite POR-SQU-POR molecule shows 2PA cross sections greater than 10(3) GM over most of the spectral range from 850 to 1600 nm (the minimum value being 780 GM at 1600 nm). The maximum value is approximately 11,000 GM near the Nd:YAG laser wavelength of 1064 nm. This broad spectral range of large 2PA cross sections is unprecedented in any other molecular system and can be explained by intramolecular charge transfer. A theoretical quantum-chemical analysis in combination with different experimental techniques allows insight into the energy-level structure and origin of the nonlinear absorption behavior of POR-SQU-POR.

Spatially resolved Raman spectra were measured on thick GaN samples with known dislocation density grown by hydride vapor phase epitaxy. The frequencies of the E 2 (high) and E 1 (transverse optical) phonons shift to lower wave number over a distance of 30 µm from the sapphire substrate/GaN interface. The shifts are linearly correlated with the dislocation density suggesting that the strain due to the lattice mismatch at the interface determines both quantities.