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Register a new userA microscopic picture of paraelectric perovskites from structural prototypes
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We show with first-principles molecular dynamics the persistence of intrinsic $langle111rangle$ Ti off-centerings for BaTiO$_3$ in its cubic paraelectric phase. Intriguingly, these are inconsistent with the known space group for this phase. Inspired by this observation, we deploy a systematic symmetry analysis to construct representative structural models in the form of supercells that satisfy a desired point symmetry but are built from the combination of lower-symmetry primitive cells. We define as structural prototypes the smallest of these that are both energetically and dynamically stable. Remarkably, two 40-atom prototypes can be identified for paraelectric BaTiO$_3$; these are also common to many other ABO$_3$ perovskites. These prototypes can offer structural models of paraelectric phases that can be used for the computational engineering of functional materials displaying such hidden order. Last, we show that the emergence of B-cation off-centerings and the consequent disappearance of the phonon instabilities is controlled by the equilibrium volume, in turn dictated by the filler A cation.
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THz-range dielectric spectroscopy and first-principle-based effective-Hamiltonian molecular dynamics simulations were employed to elucidate the dielectric response in the paraelectric phase of (Ba,Sr)TiO3 solid solutions. Analysis of the resulting dielectric spectra suggests the existence of a crossover between two different regimes: a higher-temperature regime governed by the soft mode only versus a lower-temperature regime exhibiting a coupled soft mode/central mode dynamics. Interestingly, a single phenomenological coupling model can be used to adjust the THz dielectric response in the entire range of the paraelectric phase (i.e., even at high temperature). We conclude that the central peak is associated with thermally activated processes, and that it cannot be discerned anymore in the dielectric spectra when the rate of these thermally activated processes exceeds certain characteristic frequency of the system.
Perovskites have attracted much attention due to their remarkable optical properties. While it is well established that excitons dominate their optical response, the impact of higher excitonic states and formation of phonon sidebands in optical spectra still need to be better understood. Here, we perform a theoretical study on excitonic properties of monolayered hybrid organic perovskites -- supported by temperature-dependent photoluminescence measurements. Solving the Wannier equation, we obtain microscopic access to the Rydberg-like series of excitonic states including their wavefunctions and binding energies. Exploiting the generalized Elliot formula, we calculate the photoluminescence spectra demonstrating a pronounced contribution of a phonon sideband for temperatures up to 50 K -- in agreement with experimental measurements. Finally, we predict temperature-dependent linewidths of the three energetically lowest excitonic transitions and identify the underlying phonon-driven scattering processes.
Understanding the structural underpinnings of magnetism is of great fundamental and practical interest. Se_{1-x}Te_{x}CuO_{3} alloys are model systems for the study of this question, as composition-induced structural changes control their magnetic interactions. Our work reveals that this structural tuning is associated with the position of the supposedly dummy atoms Se and Te relative to the super-exchange (SE) Cu--O--Cu paths, and not with the SE angles as previously thought. We use density functional theory, tight-binding, and exact diagonalization methods to unveil the cause of this surprising effect and hint at new ways of engineering magnetic interactions in solids.
We combine the results of magnetic and transport measurements with neutron diffraction data to construct the structural and magnetic phase diagram of the entire family of SrMn$_{1-x}$Ru$_{x}$O$_3$ ($0 leqslant x leqslant 1$) perovskites. We have found antiferromagnetic ordering of the C type for lightly Ru-substituted materials ($0.06 leqslant x leqslant 0.5$) in a similar manner to $R_{y}$Sr$_{1-y}$MnO$_3$ ($R$=La, Pr), due to the generation of Mn$^{3+}$ in both families of manganite perovskites by either $B$-site substitution of Ru$^{5+}$ for Mn$^{4+}$ or $A$-site substitution of $R^{3+}$ for Sr$^{2+}$. This similarity is driven by the same ratio of $d^4$ / $d^3$ ions in both classes of materials for equivalent substitution level. In both cases, a tetragonal lattice distortion is observed, which for some compositions ($0.06 leqslant x leqslant 0.2$) is coupled to a C-type AF transition and results in a first order magnetic and resistive transition. Heavily substituted SrMn$_{1-x}$Ru$_{x}$O$_3$ materials are ferromagnetic due to dominating exchange interactions between the Ru$^{4+}$ ions. Intermediate substitution ($0.6 leqslant x leqslant 0.7$) leads to a spin-glass behavior instead of a quantum critical point reported previously in single crystals, due to enhanced disorder.
The performance of perovskite solar cells recently exceeded 15% solar-to-electricity conversion efficiency for small-area devices. The fundamental properties of the active absorber layers, hybrid organic-inorganic perovskites formed from mixing metal and organic halides [textit{e.g.} (NH$_4$)PbI$_3$ and (CH$_3$NH$_3$)PbI$_3$], are largely unknown. The materials are semiconductors with direct band gaps at the boundary of the first Brillouin zone. The calculated dielectric response and band gaps show an orientation dependence, with a low barrier for rotation of the organic cations. Due to the electric dipole of the methylammonium cation, a photoferroic effect may be accessible, which could enhance carrier collection.
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