Linking On-State Memory and Distributed Kinetics in Single Nanocrystal Blinking

Memory effects in single nanocrystal fluorescence blinking are investigated as a function of the on-state kinetics for CdSe/ZnS quantum dots and CdSe nanorods. The on-state duration probability distributions for single nanocrystal blinking traces are characterized by an inverse power law, which crosses over to exponential decay for long on-state durations. The correlations of subsequent on-state durations (<i>R</i>_log,on) are found to decrease for nanocrystals that display earlier crossover times and smaller power law coefficients. Specifically, <i>R</i>_log,on increases from 0.14 ± 0.02 to a saturation value of 0.44 ± 0.01 for nanocrystals with average crossover times of ∼100 ms to more than 5.0 s, respectively. The results represent the first link between memory effects and blinking kinetics and are interpreted in the framework of two competing charge trapping mechanisms. A slow fluctuation-based trapping mechanism leads to power-law-distributed on durations and significant memory effects; however, the additional contribution of an ionization-induced trapping pathway is found to induce crossover to exponential decay and decreased memory. Monte Carlo simulations of nanocrystal blinking based on the two trapping mechanisms reproduce the experimental results, suggesting that the power law component and the memory effects correlate with a fluctuation-based mechanism. This effect is found to be universal, occurring for two nanocrystal morphologies and in blinking data measured using a wide range of continuous and pulsed excitation conditions

Effect of Thermal Annealing in Ammonia on the Properties of InGaN Nanowires with Different Indium Concentrations

The utility of an annealing procedure in ammonia ambient is investigated for improving the optical characteristics of In_<i>x</i>Ga_1–<i>x</i>N nanowires (0.07 ≤ <i>x</i> ≤ 0.42) grown on c-Al₂O₃ using a halide chemical vapor deposition method. Morphological studies using scanning electron microscopy confirm that the nanowire morphology is retained after annealing in ammonia at temperatures up to 800 °C. However, significant indium etching and composition inhomogeneities are observed for higher indium composition nanowires (<i>x</i> = 0.28, 0.42), as measured by energy-dispersive X-ray spectroscopy and <i>Z</i>-contrast scanning transmission electron microscopy. Structural analyses, using X-ray diffraction and high-resolution transmission electron microscopy, indicate that this is a result of the greater thermal instability of higher indium composition nanowires. The effect of these structural changes on the optical quality of InGaN nanowires is examined using steady-state and time-resolved photoluminescence measurements. Annealing in ammonia enhances the integrated photoluminescence intensity of In_<i>x</i>Ga_1–<i>x</i>N nanowires by up to a factor of 4.11 ± 0.03 (for <i>x</i> = 0.42) by increasing the rate of radiative recombination. Fitting of photoluminescence decay curves to a Kohlrausch stretched exponential indicates that this increase is directly related to a larger distribution of recombination rates from composition inhomogeneities caused by annealing. The results demonstrate the role of thermal instability on the improved optical properties of InGaN nanowires annealed in ammonia

DataSheet1_Microfluidic liquid sheets as large-area targets for high repetition XFELs.PDF

The high intensity of X-ray free electron lasers (XFELs) can damage solution-phase samples on every scale, ranging from the molecular or electronic structure of a sample to the macroscopic structure of a liquid microjet. By using a large surface area liquid sheet microjet as a sample target instead of a standard cylindrical microjet, the incident X-ray spot size can be increased such that the incident intensity falls below the damage threshold. This capability is becoming particularly important for high repetition rate XFELs, where destroying a target with each pulse would require prohibitively large volumes of sample. We present here a study of microfluidic liquid sheet dimensions as a function of liquid flow rate. Sheet lengths, widths and thickness gradients are shown for three styles of nozzles fabricated from isotropically etched glass. In-vacuum operation and sample recirculation using these nozzles is demonstrated. The effects of intense XFEL pulses on the structure of a liquid sheet are also briefly examined.</p

Light-Induced Radical Formation and Isomerization of an Aromatic Thiol in Solution Followed by Time-Resolved X‑ray Absorption Spectroscopy at the Sulfur K‑Edge

We applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ∼70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemical reaction pathways and transient products of sulfur-containing molecules in solution

Atomic-Scale Perspective of Ultrafast Charge Transfer at a Dye–Semiconductor Interface

Understanding interfacial charge-transfer processes on the atomic level is crucial to support the rational design of energy-challenge relevant systems such as solar cells, batteries, and photocatalysts. A femtosecond time-resolved core-level photoelectron spectroscopy study is performed that probes the electronic structure of the interface between ruthenium-based N3 dye molecules and ZnO nanocrystals within the first picosecond after photoexcitation and from the unique perspective of the Ru reporter atom at the center of the dye. A transient chemical shift of the Ru 3d inner-shell photolines by (2.3 ± 0.2) eV to higher binding energies is observed 500 fs after photoexcitation of the dye. The experimental results are interpreted with the aid of ab initio calculations using constrained density functional theory. Strong indications for the formation of an interfacial charge-transfer state are presented, providing direct insight into a transient electronic configuration that may limit the efficiency of photoinduced free charge-carrier generation