PACS Infrared spectra 78.30.-j; Self-trapped or small polarons 71.38 Ht; Bipolarons 71.38 Mx; Phonon interactions 63.20 K; Collective effects 71.45.-d; multiferroics 75.85.+t; Reflection and transmission coefficients, emissivity (farand mid-infrared) 78.20.Ci
AbstractWe report on the high-temperature evolution of far-and mid-infrared reflectivity and emissivity spectra of ambient orthorhombic ErMnO 3 from 12 K to sample decomposition above 1800 K. At low temperatures the number of phonons agrees with the predictions for orthorhombic space group D 2h 16 -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 O´ lower temperature cooperative phase coexists with cubicorthorhombic O. O-ErMnO 3 undergoes a first order order-disorder transition into the perovskite cubic phase at T cubic ~1329 K ± 20 K 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 T cubic the bipolaron fingerprint profile is the mid-infrared 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 consequence of dynamically sharing δ disproportioned e g electrons hovering over the JT distorted octahedral dimer [Mn (Q JT ) 3+δ (Mn(Q JT ) 3-δ ))O 6/2 ] 2 . A thermal driven insulator-metal transition is detected with onset ~1600 K. We also address the occurrence of an inhomogeneity induced THz band result of heating the samples in dry air, triggering Mn 3+ -Mn 4+ double exchange, under the presence of Mn 4+ smaller ions stabilizing the orthorhombic lattice.