Canonical spin glass and cluster glass behavior in the polymorphs of LiFeSnO4

Abstract

We report a comprehensive and comparative study of structural, static, dynamic, and nonequilibrium magnetic properties on the polymorphs of $\mathrm{LiFeSn}{\mathrm{O}}_{4}$. It exhibits two polymorphs: (i) orthorhombic phase (HT) stabilized at high temperature and (ii) hexagonal phase (LT) obtained at lower synthetic temperature. The HT phase crystallizes in the orthorhombic structure (space group: Pmcn) and exhibits a site disordered, nonfrustrated zig-zag network of ${\mathrm{Fe}}^{3+}$ and ${\mathrm{Sn}}^{4+}$ ions. On the other hand, the LT phase shows a disordered frustrated kagome network of ${\mathrm{Li}}^{1+}, {\mathrm{Fe}}^{3+}$, and ${\mathrm{Sn}}^{4+}$ ions crystallizing in the hexagonal structure (space group: $P{6}_{3}mc$). The low-temperature thermo-magnetic irreversibility and the absence of heat capacity anomaly in both polymorphs indicate the absence of long-range magnetic ordering and a possible glassy state. Zero-field-cooled and field-cooled magnetic memory effect and spin relaxation measurements stipulate the spin glass nature of the polymorphs. Further, spin glass behavior is confirmed by the AC susceptibility measurements. Interestingly, these polymorphs reveal different classes of spin glass states. The site disordered HT phase exhibits a single spin-flip time ${\ensuremath{\tau}}_{0}\ensuremath{\sim}3\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}13}$ sec, indicating a canonical spin glass state. In contrast, LT phase, which is disordered and geometrically frustrated, shows the spin-flip time of ${\ensuremath{\tau}}_{0}\ensuremath{\sim}9\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}10}$ sec, suggesting a cluster spin glass state. In addition, the exchange bias effect was observed due to magnetic inhomogeneity in both polymorphs.