Cluster Spin Glass State in Ba$_3$Sb$_{1+x}$Co$_{2-x}$O$_{9-\delta}$: Cation Disorder and Mixed-Valence Co Dimers

TL;DR

This study uncovers a cluster spin-glass state in Ba$_3$Sb$_{1+x}$Co$_{2-x}$O$_{9-\delta}$ driven by cation disorder, mixed-valence Co dimers, and geometric frustration, with evidence from magnetic, structural, and thermodynamic measurements.

Contribution

It demonstrates that cation disorder and oxygen vacancies induce a spin-glass-like state in a cobalt-based hexagonal perovskite, highlighting the role of disorder in stabilizing unconventional magnetic phases.

Findings

Frequency-dependent spin-freezing transition observed.

Absence of long-range magnetic order down to 1.5 K.

Significant Co/Sb disorder and oxygen non-stoichiometry confirmed.

Abstract

We investigate the structural, magnetic, and thermodynamic properties of \BSCO\ ($x$ = 0.04, $\delta$ = 0.54), a hexagonal perovskite featuring face-sharing CoO$_6$ octahedra that forms Co dimers. DC and AC magnetization measurements reveal a frequency-dependent spin-freezing transition consistent with glassy dynamics. AC susceptibility fits best to the Vogel-Fulcher model, indicating collective freezing of interacting spin clusters. Isothermal magnetization follows the Langevin function, suggesting finite-sized magnetic clusters rather than isolated paramagnetic moments. Non-equilibrium dynamics, evidenced by thermoremanent magnetization and memory effects, further support a spin-glass-like state. Heat capacity shows no sharp anomalies, and neutron powder diffraction confirms the absence of magnetic Bragg peaks down to 1.5~K, ruling out long-range magnetic order. Rietveld refinement reveals significant Co/Sb intersite disorder ($\sim$~30\pct) and oxygen non-stoichiometry, introducing exchange randomness and frustration that drive the spin-glass-like behavior. Electrical resistivity exhibits Arrhenius-type temperature dependence with an activation energy of 0.173~eV, consistent with semiconducting behavior. Temperature-dependent X-ray diffraction shows no structural phase transitions, confirming that the spin-glass-like state is not lattice-driven. Our results establish \BSCO\ as a cluster spin-glass candidate, where Co dimers, disorder, and geometric frustration prevent long-range order, leading to slow spin dynamics. These findings highlight the role of cation disorder and oxygen vacancies in stabilizing unconventional magnetic states in cobalt-based hexagonal perovskites.