Spin-driven Phase Transitions in ZnCr$_2$Se$_4$ and ZnCr$_2$S$_4$ Probed by High Resolution Synchrotron X-ray and Neutron Powder Diffraction

TL;DR

This study investigates the complex spin-driven phase transitions in ZnCr$_2$S$_4$ and ZnCr$_2$Se$_4$ using high-resolution diffraction, revealing magnetic and structural changes linked to frustration and external magnetic fields.

Contribution

The paper provides detailed insights into the magnetic and structural phase transitions of ZnCr$_2$S$_4$ and ZnCr$_2$Se$_4$, highlighting the role of magnetic frustration and external fields in these processes.

Findings

ZnCr$_2$Se$_4$ exhibits a first-order transition to an incommensurate helical magnetic structure at 21 K.

ZnCr$_2$S$_4$ undergoes two magnetic and structural phase transitions at 15 K and 8 K.

External magnetic fields influence the transition temperatures and induce negative thermal expansion in both compounds.

Abstract

The crystal and magnetic structures of the spinel compounds ZnCr$_2$S$_4$ and ZnCr$_2$Se$_4$ were investigated by high resolution powder synchrotron and neutron diffraction. ZnCr$_2$Se$_4$ exhibits a first order phase transition at $T_N=21$ K into an incommensurate helical magnetic structure. Magnetic fluctuations above $T_N$ are coupled to the crystal lattice as manifested by negative thermal expansion. Both, the complex magnetic structure and the anomalous structural behavior can be related to magnetic frustration. Application of an external magnetic field shifts the ordering temperature and the regime of negative thermal expansion towards lower temperatures. Thereby, the spin ordering changes into a conical structure. ZnCr$_2$S$_4$ shows two magnetic transitions at $T_{N1}=15$ K and $T_{N2}=8$ K that are accompanied by structural phase transitions. The crystal structure transforms from the cubic spinel-type (space group $Fd$\={3}$m$) at high temperatures in the paramagnetic state, via a tetragonally distorted intermediate phase (space group $I4_1$ / $amd$) for $T_{N2} < T < T_{N1}$ into a low temperature orthorhombic phase (space group $I m m a$) for $T < T_{N2}$. The cooperative displacement of sulfur ions by exchange striction is the origin of these structural phase transitions. The low temperature structure of ZnCr$_2$S$_4$ is identical to the orthorhombic structure of magnetite below the Verwey transition. When applying a magnetic field of 5 T the system shows an induced negative thermal expansion in the intermediate magnetic phase as observed in ZnCr$_2$Se$_4$.