Probing the Electronic Structure of Hybrid Perovskites in the Orientationally Disordered Cubic Phase.

Hybrid organic-inorganic lead halide perovskites are projected as new generation photovoltaic and optoelectronic materials with improved efficiencies. However, their electronic structure so far remains poorly understood, particularly in the orientationally disordered cubic phase. We performed electronic structure investigations using angle-resolved photoemission spectroscopy on two prototypical samples (MAPbBr3 and MAPbCl3) in their cubic phase, and the results are compared with the calculations within two theoretical models where MA+ is orientationally (1) disordered (MA+ ion is replaced by spherically symmetric Cs+ ion) and (2) ordered (MA oriented along (100) direction) but keeping the symmetry of the unit cell cubic. Degeneracy of the valence bands and behavior of constant energy contours are consistent with model 1, which supports strongly the disordered nature of the orientation of the MA+ ions in the cubic phase. Band structure calculations also reveal that spin-orbit coupling induced Rashba splitting is suppressed by the orientational disorder.

Self-immobilized Pd nanowires as an excellent platform for a continuous flow reactor: efficiency, stability and regeneration.

Despite extensive use of Pd nanocrystals as catalysts, the realization of a Pd-based continuous flow reactor remains a challenge. Difficulties arise due to ill-defined anchoring of the nanocrystals on a substrate and reactivity of the substrate under different reaction conditions. We demonstrate the first metal (Pd) nanowire-based catalytic flow reactor that can be used across different filtration platforms, wherein, reactants flow through a porous network of nanowires (10-1000 nm pore sizes) and the product can be collected as filtrate. Controlling the growth parameters and obtaining high aspect ratio of the nanowires (diameter = ∼13 nm and length > 8000 nm) is necessary for successful fabrication of this flow reactor. The reactor performance is similar to a conventional reactor, but without requiring energy-expensive mechanical stirring. Synchrotron-based EXAFS studies were used to examine the catalyst microstructure and Operando FT-IR spectroscopic studies were used to devise a regenerative strategy. We show that after prolonged use, the catalyst performance can be regenerated up to 99% by a simple wash-off process without disturbing the catalyst bed. Thus, collection, regeneration and redispersion processes of the catalyst in conventional industrial reactors can be avoided. Another important advantage is avoiding specific catalyst-anchoring substrates, which are not only expensive, but also non-universal in nature.

Band Structure of Topological Insulator BiSbTe1.25Se1.75.

We present our angle resolved photoelectron spectroscopy (ARPES) and density functional theory results on quaternary topological insulator (TI) BiSbTe1.25Se1.75 (BSTS) confirming the non-trivial topology of the surface state bands (SSBs) in this compound. We find that the SSBs, which are are sensitive to the atomic composition of the terminating surface have a partial 3D character. Our detailed study of the band bending (BB) effects shows that in BSTS the Dirac point (DP) shifts by more than two times compared to that in Bi2Se3 to reach the saturation. The stronger BB in BSTS could be due to the difference in screening of the surface charges. From momentum density curves (MDCs) of the ARPES data we obtained an energy dispersion relation showing the warping strength of the Fermi surface in BSTS to be intermediate between those found in Bi2Se3 and Bi2Te3 and also to be tunable by controlling the ratio of chalcogen/pnictogen atoms. Our experiments also reveal that the nature of the BB effects are highly sensitive to the exposure of the fresh surface to various gas species. These findings have important implications in the tuning of DP in TIs for technological applications.

CH3NH3PbI3, A Potential Solar Cell Candidate: Structural and Spectroscopic Investigations.

Hybrid organic-inorganic metal halides of the type CH3NH3PbX3 have emerged as potential materials for photovoltaic applications. In this paper we discuss structural, electronic, and optical spectroscopy investigations performed on high quality single crystals of CH3NH3PbI3. Our results conclusively suggest that CH3NH3PbI3 crystallizes in centrosymmetric space group and the methylammonium moiety exhibits disordered packing at room temperature. Extracted values of the exciton binding energy, the electron-phonon coupling constant, and the schematic energy level diagram constructed from the emission broadening, Raman, and photoemission spectroscopy measurements clearly show the potential of this system in photovoltaic applications.

Direct observation of large electronic domains with memory effect in doped manganites.

We use a spatially resolved, direct spectroscopic probe for electronic structure with an additional sensitivity to chemical compositions to investigate high-quality single crystal samples of La(1/4)Pr(3/8)Ca(3/8)MnO3, establishing the formation of distinct insulating domains embedded in the metallic host at low temperatures. These domains are found to be at least an order of magnitude larger in size compared to previous estimates and exhibit memory effects on temperature cycling in the absence of any perceptible chemical inhomogeneity, suggesting long-range strains as the probable origin.