Fast Fluoride Ion Conduction in Molecular Cation-Containing Compounds, NH4(Mg1-xLix)F3-x and (NH4)2(Mg1-xLix)F4-x

Aiming development of the fast anion conductors, we proposed a new material design using flexible molecular cation as a host cation, and demonstrated it with fluoride ion conduction in NH4(Mg1-xLix)F3-x and (NH4)2(Mg1-xLix)F4-x. Relatively high fluoride ion conductivities of 4.8×10-5 S cm-1 and 8.4×10-6 S cm-1 were achieved at 323 K in (NH4)2(Mg0.85Li0.15)F3.85 and NH4(Mg0.9Li0.1)F2.9, respectively. Our findings suggest molecular cation-containing compounds can be attractive material groups for fast anion conductors.

Phase Diagram and Cation Dynamics of Mixed MA1-xFAxPbBr3 Hybrid Perovskites

<p>We use a multi-technique approach to determine the phase diagram and molecular cation dynamics of mixed methylammonium-formamidinium MA1-xFAxPbBr3 (0 ≤ x ≤ 1) hybrid perovskites. The calorimetric, ultrasonic and X-ray diffraction experiments show a substantial suppression of the structural phase transitions and stabilization of the cubic phase upon mixing. We use the broadband dielectric and Raman spectroscopies to study the MA and FA cations dynamics in these compounds. The broadband dielectric spectroscopy indicates absence of the MA cation ordering and a gradual increase of the rotation barrier upon mixing. The room-temperature dielectric permittivity substantially decreases as the fraction of the FA cations is increased. No significant changes of the permittivity are detected at temperatures where the dielectric relaxations are absent. We also observe weak signatures of a dipolar glass phase for the highest mixing level (x = 0.5). The Raman spectroscopy supports the dielectric results and reveals additional subtle information about the FA cation dynamics.</p><br>

Phase Diagram and Cation Dynamics of Mixed MA1-xFAxPbBr3 Hybrid Perovskites

<p>We use a multi-technique approach to determine the phase diagram and molecular cation dynamics of mixed methylammonium-formamidinium MA1-xFAxPbBr3 (0 ≤ x ≤ 1) hybrid perovskites. The calorimetric, ultrasonic and X-ray diffraction experiments show a substantial suppression of the structural phase transitions and stabilization of the cubic phase upon mixing. We use the broadband dielectric and Raman spectroscopies to study the MA and FA cations dynamics in these compounds. The broadband dielectric spectroscopy indicates absence of the MA cation ordering and a gradual increase of the rotation barrier upon mixing. The room-temperature dielectric permittivity substantially decreases as the fraction of the FA cations is increased. No significant changes of the permittivity are detected at temperatures where the dielectric relaxations are absent. We also observe weak signatures of a dipolar glass phase for the highest mixing level (x = 0.5). The Raman spectroscopy supports the dielectric results and reveals additional subtle information about the FA cation dynamics.</p><br>

Lead-free hybrid perovskite N(CH3)4SnI3 with robust ferroelectricity induced by large and non-polar N(CH3)4+ molecular cation

The ferroelectricity in the hybrid perovskite CH3NH3PbI3 is under debate because it results from the polar molecular cation CH3NH3+ while the molecular orientation was reported to be random. Here we predict that a Pb-free hybrid perovskite N(CH3)4SnI3 with non-polar molecular cation N(CH3)4+ has strong ferroelectricity with a spontaneous polarization of 16.13 μC cm−2. The large polarization results from the distortion of SnI6 octahedron induced by the large N(CH3)4+ and is independent of the molecular orientation, so the ferroelectricity is robust. The ferroelectric R3m perovskite structure of N(CH3)4SnI3 can be synthesized as the ground state under a hydrostatic pressure over 3 GPa and remains stable under ambient pressure. Given the strong ferroelectricity, good stability and high visible-light absorption, N(CH3)4SnI3 may be an ideal light-absorber semiconductor for high-efficiency solar cells because its ferroelectric polarization can facilitate electron-hole separation and produce large bulk photovoltaic effect, making the design of homogeneous bulk photovoltaic devices possible.

Multiple rotor modes and how to trigger them: complex cation ordering in the family of relaxing hybrid formates

A combination of structural, dielectric and calorimetric studies is used to describe a highly atypical behaviour of novel hybrid formate [NH3(CH2)3NH2(CH2)3NH3][Mn(HCOO)3]3, incorporating large triprotonated molecular cation. Two successive phase transitions,...

First-principles identification of the charge-shifting mechanism and ferroelectricity in hybrid halide perovskites

Hybrid halide perovskite solar cells have recently attracted substantial attention, mainly because of their high power conversion efficiency. Among diverse variants, (CH3NH3)PbI3 and HC(NH2)2PbI3 are particularly promising candidates because their bandgap well matches the energy range of visible light. Here, we demonstrate that the large nonlinear photocurrent in β-(CH3NH3)PbI3 and α-HC(NH2)2PbI3 is mostly determined by the intrinsic electronic band properties near the Fermi level, rooted in the inorganic backbone, whereas the ferroelectric polarization of the hybrid halide perovskite is largely dominated by the ionic contribution of the molecular cation. The spatial charge shift upon excitation is attributed to the charge transfer from iodine to lead atoms in the backbone, which is independent of the presence of the cationic molecules. Our findings can serve as a guiding principle for the design of future materials for halide-perovskite solar cells with further enhanced photovoltaic performance.

6MNEP: a molecular cation with large hyperpolarizability and promise for nonlinear optical applications

The featured organic push-pull chromophores 6MNEP-T and 6MNEP-4NBS show from 1.6 to 2.5 times larger calculated macroscopic nonlinearities compared with benchmark organic nonlinear optical crystals.