<i>h</i>-ErMnO₃ absorbance, reflectivity and, emissivity in the THz to mid-infrared from 2 K to 1700 K

Abstract

We report the temperature dependent THz to mid-infrared response of hexagonal-ErMnO₃ using absorption, reflectivity, and emissivity techniques from 2 K to 1700 K. At low temperatures, lowest frequency vibrational modes which extend up the lock-in ferroelectric temperature, coexist with paramagnon excitations and are associated with well-defined crystal field Rare Earth pure magnetic replicas in an intriguing phonon-magnetic convergence enhancing the multiferroic character of <i>h</i>-ErMnO₃. Increasing the temperature, a number of vibrational bands close to the space group predicted undergo profile broadening and softening. In particular, a distinctive set of bands in the 288-329 cm^-1 (300 K) range has a component whose profile is carrier screened becoming nearly fully blurred in the intermediate phase between ~830 K and ~1500 K. Below TC ~830 K this asymmetric band, having one component still partially screened, further splits as spin phonon interaction and the tripling of the unit cell takes place revealing at TN ~79 K a delicate balance of long- and short-range interactions. Ambient Raman scattering brings up evidence of a Fröhlich resonance due to Coulomb interactions between carriers and the macroscopic field linked to the corresponding longitudinal optical phonon mode. We found it is dynamically correlated to the hexagonal c-axis negative thermal expansion. Quantitative analyses of the mid-infrared (MIR) optical conductivity show that also plays a role in small polarons and mediates in high temperature bipolarones. Bipolaron profiles at high temperatures change as the sample opacity increases when at ~900 K straight stripes turn curly toward complex vortex-antivortex domain patterns in the paraelectric phase. At still higher temperatures a low frequency Drude contribution is triggered by electron hopping signaling an insulator-metal phase transition at ~1600 K while the MIR response suggests coexistence between single small polarons and bipolarons. On closing, we draw a parallel with improper ferroelectrics sustaining a lattice incommensurate intermediate phase and unit cell tripling. We argue that in the <i>h</i>-ErMnO₃ (R=Rare Earth, Y) family of compounds the intermediate phase be considered incommensurate with onset at TINC ~1500 K and ferroelectric lock-in at TC ~830 K delimiting this regime in <i>h</i>-ErMnO₃.