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Origin of Ferroelectricity in Two Prototypical Hybrid Organic–Inorganic Perovskites
journal contributionposted on 2022-01-10, 15:12 authored by Kai Li, Zhi-Gang Li, Jun Xu, Yan Qin, Wei Li, Alessandro Stroppa, Keith T. Butler, Christopher J. Howard, Martin T. Dove, Anthony K. Cheetham, Xian-He Bu
Hybrid organic–inorganic perovskite (HOIP) ferroelectrics are attracting considerable interest because of their high performance, ease of synthesis, and lightweight. However, the intrinsic thermodynamic origins of their ferroelectric transitions remain insufficiently understood. Here, we identify the nature of the ferroelectric phase transitions in displacive [(CH3)2NH2][Mn(N3)3] and order–disorder type [(CH3)2NH2][Mn(HCOO)3] via spatially resolved structural analysis and ab initio lattice dynamics calculations. Our results demonstrate that the vibrational entropy change of the extended perovskite lattice drives the ferroelectric transition in the former and also contributes importantly to that of the latter along with the rotational entropy change of the A-site. This finding not only reveals the delicate atomic dynamics in ferroelectric HOIPs but also highlights that both the local and extended fluctuation of the hybrid perovskite lattice can be manipulated for creating ferroelectricity by taking advantages of their abundant atomic, electronic, and phononic degrees of freedom.
vibrational entropy changerotational entropy changelattice dynamics calculationsintrinsic thermodynamic originshybrid perovskite latticedisplacive [( chattracting considerable interestab initio delicate atomic dynamicsalso contributes importantlyferroelectric phase transitions2 subalso highlightsabundant atomicferroelectric transitionferroelectric hoipstaking advantagesresults demonstratephononic degreeslatter alonghigh performanceextended fluctuation