Due to the unprecedented rapid increase of their power conversion efficiency, hybrid organic-inorganic perovskites CH 3 NH 3 PbX 3 (X = I, Br, Cl) can potentially revolutionize the world of solar cells. However, despite tremendous research activity, the origin of the exceptionally large diffusion length of their photogenerated charge carriers, that is, their low recombination rate, remains elusive. Using frequency and temperature-dependent dielectric measurements across the entire frequency spectrum, it is shown that the dielectric constant conserves very high values (>27) for frequencies below 1 THz in all three halides. This efficiently prevents photocarrier trapping and their recombination owing to the strong screening of charged entities. By combining ultrasonic and Raman spectroscopy with dielectric analysis, similarly large contributions to the dielectric constant are attributed to the dipolar disorder of the CH 3 NH 3 + cations as well as lattice dynamics in the gigahertz range yielding dielectric constants of ε stat = 62 for the iodide, 58 for the bromide, and about 45 for the chloride below 1 GHz at room temperature. Disorder continuously reduces for decreasing temperature. Dipole dynamics prevail in the intermediate tetragonal phase. The low-temperature orthorhombic state is antipolar. No indications of ferroelectricity are found.
Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles.
The interaction between soft optic and acoustic phonons was investigated for Sn2P2(Se0.28S0.72)6 proper uniaxial ferroelectrics by Brillouin scattering and ultrasonic pulse-echo techniques. The elastic softening of hypersound velocity of transverse acoustic phonons and for both longitudinal and transverse ultrasound waves which propagate near direction of the modulation wave vector (in the incommensurate phase at x > xLP ) was found at cooling to the Lifshitz point in the paraelectric phase. The strong increase of the ultrasound attenuation have also been observed. Such phenomena are related to the linear interaction of the soft optic and acoustic branches in the region of relatively short-range hypersound waves and to the strongly developed long-range order parameter fluctuations in the ultrasound frequency range. The hypersound velocity temperature dependence was described within the Landau-Khalatnikov approximation for the ferroelectric phase.
The spontaneous electric polarization of methylhydrazinium zinc formate occurs due to freezing of motion around the 2- and 3-axes of the methylhydrazinium cation.
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