Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O3: Polarons and bipolarons

• Autores: Massa, Nestor Emilio; Del Campo, Leire; Holldack, Karsten; Ta Phuoc, Vinh; Echegut, Patrick; Kayser, Paula; Alonso, José Antonio
• Año de publicación: 2018
• Idioma: inglés
• Tipo de recurso: artículo
• Materia: CUBIC ErMnO3; JAHN-TELLER; LATTICE DYNAMICS; POLARONS
• Institución: Consejo Nacional de Investigaciones Científicas y Técnicas

We report on the high-temperature evolution of far- and mid-infrared reflectivity and emissivity spectra of ambient orthorhombic ErMnO3 from 12 K to sample decomposition above 1800 K. At low temperatures the number of phonons agrees with the predictions for orthorhombic space group D2h16-Pbnm (Z=4) and coexists with a paramagnon spin resonance and rare-earth crystal-field transitions. Increasing the temperature, a number of vibrational bands undergo profile broadening and softening approaching the orbital disordered phase where the orthorhombic Ó lower-temperature cooperative phase coexists with cubic-orthorhombic O. O-ErMnO3 undergoes a first-order order-disorder transition into the perovskite cubic phase at Tcubic∼1329K±20K where the three triple degenerate phonons allowed by the space group Pm-3m (Z=1) are identified. At about 800 K, a quantitative small polaron analysis of the orthorhombic midinfrared real part optical conductivity shows that antisymmetric and symmetric breathing modes sustain the strongest electron-phonon interactions. Above Tcubic the bipolaron fingerprint profile is the midinfrared dominant and only feature. Its appearance correlates with the localized screening of the highest vibrational mode reststrahlen band. We propose that the longitudinal optical mode macroscopic field screening is a consequence of dynamically sharing δ disproportioned eg electrons hovering over the Jahn-Teller distorted octahedral dimer {Mn(QJT)3+δ[Mn(QJT)[3]-δ]O6/2}2. A thermal driven insulator-metal transition is detected with onset ∼1600 K. We also address the occurrence of an inhomogeneity induced terahertz band result of heating the samples in dry air, triggering Mn3+-Mn4+ double exchange, under the presence of Mn4+ smaller ions stabilizing the orthorhombic lattice.
Fil: Massa, Nestor Emilio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Del Campo, Leire. Université d Orléans; Francia
Fil: Holldack, Karsten. Institut für Methoden und Instrumentierung der Forschung mit Synchrotronstrahlung; Alemania
Fil: Ta Phuoc, Vinh. Universite de Tours; Francia
Fil: Echegut, Patrick. Centre National de la Recherche Scientifique; Francia
Fil: Kayser, Paula. University of Edinburgh; Reino Unido
Fil: Alonso, José Antonio. Instituto de Ciencia de Materiales de Madrid; España