arXiv subjects

M. Tyagi

Publications and source records attributed to M. Tyagi.

3 recordsLinked to original sources

arXiv2022

Influence of the Halide Ion on the A Site Dynamics in FAPbX3 (X = Br and Cl)

The optoelectronic properties and ultimately photovoltaic performance of hybrid lead halide perovskites, is inherently related to the dynamics of the organic cations. Here we report on the dynamics of the formamidinium (FA) cation in FAPbX3 perovskites for chloride and bromide varieties, as studied by neutron spectroscopy. Elastic fixed window scan measurements showed the onset of reorientational motion of FA cations in FAPbCl3 to occur at a considerably higher temperature compared to that in FAPbBr3. In addition, we observed two distinct dynamical transitions only in the chloride system, suggesting a significant variation in the reorientational motions of the FA cation with temperature. Quasielastic neutron scattering data analysis of FAPbCl3 showed that in the low temperature orthorhombic phase, FA cations undergo 2-fold jump reorientations about the C-H axis which evolve into an isotropic rotation in the intermediate tetragonal and high temperature cubic phases. Comparing the results with those from FAPbBr3, reveal that the time scale, barrier to reorientation and the geometry of reorientational motion of the FA cation are significantly different for the two halides. We note that this dependence of the dynamic properties of the A-site cation on the halide, is unique to the FA series; the geometry of methylammonium (MA) cation dynamics in MAPbX3 is known to be insensitive to different halides.

cond-mat.mtrl-sci↗

arXiv2017

Short Time and Structural Dynamics in Polypropylene Glycol Nanocomposite

The dynamics of polypropylene glycol, both neat and attached to silica nanoparticles, were investigated using elastic neutron backscattering and dielectric spectroscopy. The mean square displacement measured by the former is suppressed by the particles at temperatures corresponding to a dielectric secondary relaxation (that involves only a portion of the repeat unit) and the segmental relaxation (glass transition). Despite the suppression of the displacements, the motions are faster in the nanocomposite, primarily due to poorer packing (lower density) at the particle interface. At very low temperatures we discovered a new dynamic process in the polymer. Reflecting its very local nature, this process is unaffected by attachment of the chains to the silica.

cond-mat.soft↗

arXiv2015

Rotational Dynamics of Organic Cations in CH3NH3PbI3 Perovskite

Methylammonium lead iodide (CH3NH3PbI3) based solar cells have shown impressive power conversion efficiencies of above 20%. However, the microscopic mechanism of the high photovoltaic performance is yet to be fully understood. Particularly, the dynamics of CH3NH3+ cations and their impact on relevant processes such as charge recombination and exciton dissociation are still poorly understood. Here, using elastic and quasi-elastic neutron scattering techniques and group theoretical analysis, we studied rotational modes of the CH3NH3+ cation in CH3NH3PbI3. Our results show that, in the cubic (T > 327K) and tetragonal (165K < T < 327K) phases, the CH3NH3+ ions exhibit four-fold rotational symmetry of the C-N axis (C4) along with three-fold rotation around the C-N axis (C3), while in orthorhombic phase (T < 165K) only C3 rotation is present. Around room temperature, the characteristic relaxation times for the C4 rotation is found to be ps while for the C3 rotation ps. The -dependent rotational relaxation times were fitted with Arrhenius equations to obtain activation energies. Our data show a close correlation between the C4 rotational mode and the temperature dependent dielectric permittivity. Our findings on the rotational dynamics of CH3NH3+ and the associated dipole have important implications on understanding the low exciton binding energy and slow charge recombination rate in CH3NH3PbI3 which are directly relevant for the high solar cell performance.

cond-mat.mtrl-sci↗