Resolving growth-induced off-stoichiometry in AgCrSe$_2$ single crystals

Abstract

The layered delafossite-like antiferromagnet AgCrSe$_2$ is a superionic conductor at high temperatures and has been reported to exhibit anomalous Hall behavior and Kondo physics at low temperatures. These extraordinary transport properties have been established almost exclusively on single crystals grown by chemical vapor transport, raising questions about the role of growth-induced off-stoichiometry. Using elemental analysis, single-crystal X-ray diffraction, and magnetization measurements, we show that such crystals are indeed systematically off-stoichiometric, with a general composition of Ag$_{1-x}$Cr(Se$_{2-y}$Cl$_y$) ($x \approx y \approx 0.08$) arising from the use of CrCl$_3$ as a transport agent. This off-stoichiometry manifests in altered magnetic properties, most notably a suppressed N\'{e}el temperature of 46\,K compared to 58\,K in stoichiometric polycrystalline samples prepared by solid-state synthesis. By optimizing an Ag/Se self-flux growth method, we obtained large single crystals of AgCrSe$_2$ that recover the magnetic transition temperature and saturation field of stoichiometric powder samples. These results establish self-flux growth as a route to high-quality stoichiometric AgCrSe$_2$ single crystals and provide a reliable platform for reassessing whether the reported anomalous transport phenomena are intrinsic or arise from off-stoichiometry.