Observation of robust spin-phonon coupling and indication of hidden structural transition in the spin-driven ferroelectrics Mn4B_2O_9 (B= Nb, Ta)

Abstract

We report detailed Raman spectroscopic and magnetic susceptibility studies on the spin-driven ferroelectric compounds Mn4Nb2O9 (MNO) and Mn4Ta2O9 (MTO). Both systems exhibit strong spin-phonon coupling below the short-range magnetic ordering temperature (T(sro)=223 K), followed by further renormalization of several Raman modes at the long-range magnetic ordering temperatures (TN = 120 K for MNO and 110 K for MTO). Pronounced anomalies in Raman mode frequencies and linewidths, along with the emergence of octahedral modes between Tsro and TN, indicate a possible low-symmetry structural transition, more evident in MNO and closely linked to magnetic ordering in MTO. Distinct low-temperature evolutions of Raman mode shift, linewidth, and integrated intensity in MNO and MTO highlight the role of the nonmagnetic B-site cation in tuning spin-lattice coupling, driven by differences in spin-orbit coupling and orbital hybridization between Nb5+ (4d) and Ta5+ (5d). By combining Raman spectroscopy with nuclear magnetic resonance, and diffuse reflectance spectroscopy, we further show that Mn-based systems possess a more distorted local structure than their Co analogues, while their electronic structures differ despite comparable band gaps. These results provide a comprehensive understanding of spin-lattice coupling in Mn- and Co-based A4B2O9 magnetoelectric systems.