Charge-Carrier Recombination in Halide Perovskites.

The success of halide perovskites in a host of optoelectronic applications is often attributed to their long photoexcited carrier lifetimes, which has led to charge-carrier recombination processes being described as unique compared to other semiconductors. Here, we integrate recent literature findings to provide a critical assessment of the factors we believe are most likely controlling recombination in the most widely studied halide perovskite systems. We focus on four mechanisms that have been proposed to affect measured charge carrier recombination lifetimes, namely: (1) recombination via trap states, (2) polaron formation, (3) the indirect nature of the bandgap (e.g., Rashba effect), and (4) photon recycling. We scrutinize the evidence for each case and the implications of each process on carrier recombination dynamics. Although they have attracted considerable speculation, we conclude that multiple trapping or hopping in shallow trap states, and the possible indirect nature of the bandgap (e.g., Rashba effect), seem to be less likely given the combined evidence, at least in high-quality samples most relevant to solar cells and light-emitting diodes. On the other hand, photon recycling appears to play a clear role in increasing apparent lifetime for samples with high photoluminescence quantum yields. We conclude that polaron dynamics are intriguing and deserving of further study. We highlight potential interdependencies of these processes and suggest future experiments to better decouple their relative contributions. A more complete understanding of the recombination processes could allow us to rationally tailor the properties of these fascinating semiconductors and will aid the discovery of other materials exhibiting similarly exceptional optoelectronic properties.EPSRC DTP Studentshi

Thermal excitation of heavy nuclei with 5-15 GeV/c antiproton, proton and pion beams

Excitation-energy distributions have been derived from measurements of 5.0-14.6 GeV/c antiproton, proton and pion reactions with $^{197}$Au target nuclei, using the ISiS 4$\pi$ detector array. The maximum probability for producing high excitation-energy events is found for the antiproton beam relative to other hadrons, $^3$He and $\bar{p}$ beams from LEAR. For protons and pions, the excitation-energy distributions are nearly independent of hadron type and beam momentum above about 8 GeV/c. The excitation energy enhancement for $\bar{p}$ beams and the saturation effect are qualitatively consistent with intranuclear cascade code predictions. For all systems studied, maximum cluster sizes are observed for residues with E*/A $\sim$ 6 MeV.Comment: 14 pages including 5 figures and 1 table. Accepted in Physics Letter B. also available at http://nuchem.iucf.indiana.edu

Au-Ag template stripped pattern for scanning probe investigations of DNA arrays produced by Dip Pen Nanolithography

We report on DNA arrays produced by Dip Pen Nanolithography (DPN) on a novel Au-Ag micro patterned template stripped surface. DNA arrays have been investigated by atomic force microscopy (AFM) and scanning tunnelling microscopy (STM) showing that the patterned template stripped substrate enables easy retrieval of the DPN-functionalized zone with a standard optical microscope permitting a multi-instrument and multi-technique local detection and analysis. Moreover the smooth surface of the Au squares (abput 5-10 angstrom roughness) allows to be sensitive to the hybridization of the oligonucleotide array with label-free target DNA. Our Au-Ag substrates, combining the retrieving capabilities of the patterned surface with the smoothness of the template stripped technique, are candidates for the investigation of DPN nanostructures and for the development of label free detection methods for DNA nanoarrays based on the use of scanning probes.Comment: Langmuir (accepted

Micro-fabrication of Carbon Structures by Pattern Miniaturization in Resorcinol-Formaldehyde Gel

A simple and novel method to fabricate and miniaturize surface and sub-surface micro-structures and micro-patterns in glassy carbon is proposed and demonstrated. An aqueous resorcinol-formaldehyde (RF) sol is employed for micro-molding of the master-pattern to be replicated, followed by controlled drying and pyrolysis of the gel to reproduce an isotropically shrunk replica in carbon. The miniaturized version of the master-pattern thus replicated in carbon is about one order of magnitude smaller than original master by repeating three times the above cycle of molding and drying. The micro-fabrication method proposed will greatly enhance the toolbox for a facile fabrication of a variety of Carbon-MEMS and C-microfluidic devices.Comment: 16 pages, 5 figure

Electrophilic Cyclopentenone Neuroprostanes Are Anti-inflammatory Mediators Formed from the Peroxidation of the ω -3 Polyunsaturated Fatty Acid Docosahexaenoic Acid.

The omega-3 polyunsaturated fatty acid docosahexaenoic acid (DHA) possesses potent anti-inflammatory properties and has shown therapeutic benefit in numerous inflammatory diseases. However, the molecular mechanisms of these anti-inflamma- tory properties are poorly understood. DHA is highly suscepti- ble to peroxidation, which yields an array of potentially bioac- tive lipid species. One class of compounds are cyclopentenone neuroprostanes (A4/J4-NPs), which are highly reactive and similar in structure to anti-inflammatory cyclopentenone prostaglandins. Here we show that a synthetic A4/J4-NP, 14-A4-NP (A4-NP), potently suppresses lipopolysaccharide- induced expression of inducible nitric-oxide synthase and cyclooxygenase-2 in macrophages. Furthermore, A4-NP blocks lipopolysaccharide-induced NF-KB activation via inhibition of I kinase-mediated phosphorylation of IKB. Mutation on Ik kinase b-cysteine 179 markedly diminishes the effect of A4-NP, suggesting that A4-NP acts via thiol mod- ification at this residue. Accordingly, the effects of A4-NP are independent of peroxisome proliferator-activated receptor-gamma and are dependent on an intact reactive cyclopentenone ring. Interestingly, free radical-mediated oxidation of DHA greatly enhances its anti-inflammatory potency, an effect that closely parallels the formation of A4/J4-NPs. Furthermore, chemical reduction or conjugation to glutathione, both of which elim- inate the bioactivity of A4-NP, also abrogate the anti-inflam- matory effects of oxidized DHA. Thus, we have demonstrated that A4/J4-NPs, formed via the oxidation of DHA, are potent inhibitors of NF-kB signaling and may contribute to the anti- inflammatory actions of DHA. These findings have implica- tions for understanding the anti-inflammatory properties of omega-3 fatty acids, and elucidate novel interactions between lipid peroxidation products and inflammation

Signals for a Transition from Surface to Bulk Emission in Thermal Multifragmentation

Excitation-energy-gated two-fragment correlation functions have been studied between 2 to 9A MeV of excitation energy for equilibrium-like sources formed in $\pi^-$ and p + $^{197}$Au reactions at beam momenta of 8,9.2 and 10.2 GeV/c. Comparison of the data to an N-body Coulomb-trajectory code shows a decrease of one order of magnitude in the fragment emission time in the excitation energy interval 2-5A MeV, followed by a nearly constant breakup time at higher excitation energy. The observed decrease in emission time is shown to be strongly correlated with the increase of the fragment emission probability, and the onset of thermally-induced radial expansion. This result is interpreted as evidence consistent with a transition from surface-dominated to bulk emission expected for spinodal decomposition.Comment: 11 pages including 3 postscript figures (1 color

Design Rules for Obtaining Narrow Luminescence from Semiconductors Made in Solution

Solution-processed semiconductors are in demand for presentandnext-generation optoelectronic technologies ranging from displaysto quantum light sources because of their scalability and ease ofintegration into devices with diverse form factors. One of the centralrequirements for semiconductors used in these applications is a narrowphotoluminescence (PL) line width. Narrow emission line widths areneeded to ensure both color and single-photon purity, raising thequestion of what design rules are needed to obtain narrow emissionfrom semiconductors made in solution. In this review, we first examinethe requirements for colloidal emitters for a variety of applicationsincluding light-emitting diodes, photodetectors, lasers, and quantuminformation science. Next, we will delve into the sources of spectralbroadening, including "homogeneous" broadening fromdynamical broadening mechanisms in single-particle spectra, heterogeneousbroadening from static structural differences in ensemble spectra,and spectral diffusion. Then, we compare the current state of theart in terms of emission line width for a variety of colloidal materialsincluding II-VI quantum dots (QDs) and nanoplatelets, III-VQDs, alloyed QDs, metal-halide perovskites including nanocrystalsand 2D structures, doped nanocrystals, and, finally, as a point ofcomparison, organic molecules. We end with some conclusions and connections,including an outline of promising paths forward

Photo-induced halide redistribution in organic-inorganic perovskite films.

Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. Our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance