Spin-driven phase transitions inZnCr2Se4andZnCr2S4probed by high-resolution synchrotron x-ray and neutron powder diffraction

Abstract

The crystal and magnetic structures of the spinel compounds ${\text{ZnCr}}_{2}{\text{S}}_{4}$ and ${\text{ZnCr}}_{2}{\text{Se}}_{4}$ were investigated by high-resolution powder synchrotron and neutron diffraction. ${\text{ZnCr}}_{2}{\text{Se}}_{4}$ exhibits a first-order phase transition at ${T}_{N}=21\text{ }\text{K}$ 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 toward lower temperatures. Thereby, the spin ordering changes into a conical structure. ${\text{ZnCr}}_{2}{\text{S}}_{4}$ shows two magnetic transitions at ${T}_{N1}=15\text{ }\text{K}$ and ${T}_{N2}=8\text{ }\text{K}$ that are accompanied by structural phase transitions. The crystal structure transforms from the cubic spinel-like (space group $Fd\overline{3}m$) at high temperatures in the paramagnetic state, via a tetragonally distorted intermediate phase (space group $I{4}_{1}/amd$) for ${T}_{N2}lTl{T}_{N1}$ into a low-temperature orthorhombic phase (space group $Imma$) for $Tl{T}_{N2}$. The cooperative displacement of sulfur ions by exchange striction is the origin of these structural phase transitions. The low-temperature structure of ${\text{ZnCr}}_{2}{\text{S}}_{4}$ 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 ${\text{ZnCr}}_{2}{\text{Se}}_{4}$.