Role of native point defects and Hg impurities in the electronic properties of Bi${}_4$I${}_4$

Abstract

We studied the effects of point defects and Hg impurities in the electronic properties of bismuth iodide (Bi${}_4$I${}_4$). Our transport measurements after annealing at different temperatures show that the resistivity of Bi${}_4$I${}_4$ depends on its thermal history, suggesting that the formation of native defects and impurities can shape the temperature dependence of electrical resistivity. Our density functional theory calculations indicate that the bismuth and iodine antisites, and bismuth vacancies are the dominant native point defects. We find that bismuth antisites introduce resonant states in the band-edges, while iodine antisites and bismuth vacancies lead to a $n$-type and $p$-type doping of Bi${}_4$I${}_4$, respectively. The Hg impurities are likely to be found at Bi substitutional sites, giving rise to the $p$-type doping of Bi${}_4$I${}_4$. Overall, our findings indicate that the presence of native point defects and impurities can significantly modify the electronic properties, and, thus, impact the resistivity profile of Bi${}_4$I${}_4$ due to modifications in the amount and type of carriers, and the associated defect(impurity) scattering. Our results suggest possible routes for pursuing fine-tuning of the electronic properties of quasi-one-dimensional quantum materials.