Symmetry breaking and unconventional charge ordering in single crystal Na2.7Ru4O9

Abstract

The interplay of charge, spin, and lattice degrees of freedom in matter leads to various forms of ordered states through phase transitions. An important subclass of these phenomena of complex materials is charge ordering (CO), mainly driven by mixed-valence states. We discovered by combining the results of electrical resistivity ($\rho$), specific heat, susceptibility $\chi$ (\textit{T}), and single crystal x-ray diffraction (SC-XRD) that Na$_{2.7}$Ru$_4$O$_9$ with the monoclinic tunnel type lattice (space group $C$2/$m$) exhibits an unconventional CO at room temperature while retaining metallicity. The temperature-dependent SC-XRD results show successive phase transitions with super-lattice reflections at \textbf{q}$_1$=(0, $\frac{1}{2}$, 0) and \textbf{q}$_2$=(0, $\frac{1}{3}$, $\frac{1}{3}$) below $T_{\textrm{C2}}$ (365 K) and only at \textbf{q}$_1$=(0, $\frac{1}{2}$, 0) between $T_{\textrm{C2}}$ and $T_{\textrm{C1}}$ (630 K). We interpreted these as an evidence for the formation of an unconventional CO. It reveals a strong first-order phase transition in the electrical resistivity at $T_{\textrm{C2}}$ (cooling) = 345 K and $T_{\textrm{C2}}$ (heating) = 365 K. We argue that the origin of the phase transition is due to the localized 4$d$ Ru-electrons. The results of our finding reveal an unique example of Ru$^{3+}$/Ru$^{4+}$ mixed valance heavy \textit{d}$^4$ ions.