Field-induced spin-flop in antiferromagnetic semiconductors with commensurate and incommensurate magnetic structures: Li2FeGeS4 (LIGS) and Li2FeSnS4 (LITS)

Inorg Chem. 2014 Dec 1;53(23):12265-74. doi: 10.1021/ic5011693. Epub 2014 Nov 14.

Abstract

Li2FeGeS4 (LIGS) and Li2FeSnS4 (LITS), which are among the first magnetic semiconductors with the wurtz-kesterite structure, exhibit antiferromagnetism with TN ≈ 6 and 4 K, respectively. Both compounds undergo a conventional metamagnetic transition that is accompanied by a hysteresis; a reversible spin-flop transition is dominant. On the basis of constant-wavelength neutron powder diffraction data, we propose that LIGS and LITS exhibit collinear magnetic structures that are commensurate and incommensurate with propagation vectors km = [1/2, 1/2, 1/2] and [0, 0, 0.546(1)], respectively. The two compounds exhibit similar magnetic phase diagrams, as the critical fields are temperature-dependent. The nuclear structures of the bulk powder samples were verified using time-of-flight neutron powder diffraction along with synchrotron X-ray powder diffraction. (57)Fe and (119)Sn Mössbauer spectroscopy confirmed the presence of Fe(2+) and Sn(4+) as well as the number of crystallographically unique positions. LIGS and LITS are semiconductors with indirect and direct bandgaps of 1.42 and 1.86 eV, respectively, according to optical diffuse-reflectance UV-vis-NIR spectroscopy.