The Conduction Band of HfS₃and Comparison with other Quasi-1D-Transition Metal Trichalcogenides: TiS₃and ZrS₃

Abstract: A comparison study of X-ray absorption spectroscopy (XAS) and density functional theory (DFT) has been used to understand the unoccupied energy states of HfS₃. The XAS spectra at Hf 4d and S 2p core level edges indicate that the bottom of the conduction band of HfS₃ is extremely sulfur weighted but also has strong hybridization between Hf-d and S-p orbitals. The density functional theory shows good agreement with the experimental results. Prior studies on TiS₃ and ZrS₃ have evidence of transition metal-sulfur hybridized conduction band bottom, which is Ti weighted in case of TiS₃ and S weighted in case of ZrS₃ [1], but there are indications that the orbital hybridization between Hf and S is stronger than in either TiS₃ or ZrS₃. This shows how the Group- IV transition metals, namely, titanium (Ti), zirconium (Zr) and hafnium (Hf), exhibit variations in their elemental contribution to the conduction and valence bands of the Janus layered trisulfide compounds.

References

[1] S. J. Gilbert, H. Yi, T. Paudel, A. Lipatov, A. J. Yost, A. Sinitskii, E. Y. Tsymbal, J. Avila, M. C. Asensio, P. A. Dowben, J. of Phys. Chem. C (2022), DOI: 10.1021/acs.jpcc.2c05589