Superfluorescence from Electron-Hole Plasma at Moderate Temperatures of 175 K.

Superfluorescence, a cooperative coherent spontaneous emission, is of great importance to the understanding of many-body correlation in optical processes. Even though superfluorescence has been demonstrated in many diverse systems, it is hard to observe in electron-hole plasma (EHP) due to its rapid dephasing and hence needs strong magnetic fields or complex microcavities. Herein, we report the first experimental observation of superfluorescence from EHP up to a moderate temperature of 175 K without external stimuli in a coupled metal halide perovskite quantum dots film. The EHP exhibits macroscopic quantum coherence through spontaneous synchronization. The coherence of the excited state decays by superfluorescence, which is redshifted 40 meV from the spontaneous emission with a ∼1700 times faster decay rate and exhibits quadratic fluence dependence. Notably, the excited state population's delayed growth and abrupt decay, which are strongly influenced by the pump fluence and the Burnham-Chiao ringing, are the characteristics of the superfluorescence. Our findings will open up a new frontier for cooperative emission and light beam-based technologies.

Don't Let the Lead Out: New Material Chemistry Approaches for Sustainable Lead Halide Perovskite Solar Cells.

Lead halide perovskites are seriously considered for next generation photovoltaic technology. They have a unique combination of easy synthesis, high efficiency, and cost-effective techniques. Still, the major concern is the toxicity of lead used in perovskite devices. The research community is still debating whether the amount of lead used in a solar cell really poses a danger or not. However, it is pretty clear that mitigating the lead leakage from the lead halide perovskite device is of utmost importance. In this review, we discuss new material chemistry approaches that can be applied to reduce the lead leakage/wastage from damaged lead halide perovskite solar cells. ECR (encapsulate, capture, and recycle) approaches have the potential to significantly reduce the environmental and health hazard risks of lead halide perovskite devices. Encapsulation by a self-healing material and rigid glass can help the perovskite survive the extreme conditions and avoid exposure of the perovskite layer to the external environment. Capturing of lead can also be done by an encapsulant layer that can very quickly and efficiently bind to lead, in the case that it leaks from the damaged perovskite device. Moreover, the recycling of damaged or decommissioned devices helps to avoid the lead wastage and contamination in the environment. Finally, we also discuss the potential of lead-free perovskite for optoelectronic applications.

Role of hydrogen bonds in molecular packing of photoreactive crystals: templating photodimerization of protonated stilbazoles in crystalline state with a combination of water molecules and chloride ions.

A difference in photobehavior and molecular packing between hydrated and anhydrous crystals of protonated trans-stilbazoles has been identified. While stilbazoles are not photoreactive in the crystalline state, upon protonation with HCl in the solid state they dimerized to a single dimer (anti-head-tail) when exposed to UV light. In these photoreactive crystals the protonated stilbazole molecules are arranged in a ladder-like format with the rungs made up of water molecules and chloride ions. A combination of water and chloride ion holds the protonated trans-stilbazoles through either N-HO or N-HCl(-) interactions. Anhydrous protonated stilbazole crystals prepared by heating the 'wet' crystals under reduced pressure were inert upon exposure to UV light. As per X-ray crystal structure analyses these light stable crystals did not contain water molecules in their lattice. The current investigation has established that water molecules are essential for photodimerization of crystalline protonated trans-stilbazoles. To compare the reactivity of protonated trans-stilbazoles with that of protonated cis-stilbazoles, photoreactivity and packing arrangement of cis-4-iodo stilbazole·HCl salt was examined. This molecule in the crystalline state only isomerized to the trans isomer and did not dimerize. Thus, while the trans isomer dimerized and did not isomerize, the cis isomer only isomerized and did not dimerize in the crystalline state. To probe the role of cationπ interaction in the packing of protonated trans-stilbazoles, energies of various types of packing in the gas phase were estimated by MP-2 calculations and cationπ interaction was found to be unimportant in the packing of protonated trans-stilbazole crystals investigated here.

Synthesis, characterization, guest inclusion, and photophysical studies of gold nanoparticles stabilized with carboxylic acid groups of organic cavitands.

Water-soluble gold nanoparticles (AuNP) stabilized with cavitands having carboxylic acid groups have been synthesized and characterized by a variety of techniques. Apparently, the COOH groups similar to thiol are able to prevent aggregation of AuNP. These AuNP were stable either as solids or in aqueous solution. Most importantly, these cavitand functionalized AuNP were able to include organic guest molecules in their cavities in aqueous solution. Just like free cavitands (e.g., octa acid), cavitand functionalized AuNP includes guests such as 4,4'-dimethylbenzil and coumarin-1 through capsule formation. The exact structure of the capsular assembly is not known at this stage. Upon excitation there is communication between the excited guest present in the capsule and gold atoms and this results in quenching of phosphorescence from 4,4'-dimethylbenzil and fluorescence from coumarin-1.

Photochemical reaction containers as energy and electron-transfer agents.

Two deep cavity cavitands, octa acid and resorcinol-capped octa acid, have been established to be good triplet energy donors in the excited state and electron donors in the ground state to excited acceptors. This property endows them the capacity to be "active" reaction containers. The above recognition provides opportunities to investigate the excited state chemistry of host-encapsulated guests without the use of secondary triplet energy and electron donors.

Photodimerization of HCl salts of azastilbenes in the solid state.

A simple strategy that is based on conversion of an electron-rich pyridyl to an electron-deficient pyridinium ion is able to orient thirteen of the sixteen olefins investigated towards a single dimer in quantitative yield in the crystalline state. The reagent used is HCl, the method involves grinding the olefin with a drop of HCl and the dimerization is achieved by exposure of the crystalline stilbazolium·HCl salts to light. The weak force involved in modifying the crystal packing is most likely charge-transfer interaction.