TY - JOUR

T1 - Hybrid lead triiodide perovskites with unsaturated heterocyclic cations containing N, O, and S atoms

T2 - Ab initio study

AU - Kevorkyants, R.

AU - Emeline, A.V.

AU - Bahnemann, D.W.

N1 - Funding information: The authors acknowledge St. Petersburg State University for the research grant (Pure ID 39054581 ). The authors also thank the Center for Computational Resources of St. Petersburg State University (Peterhof campus) for the provided CPU time. Appendix A

PY - 2020/2

Y1 - 2020/2

N2 - We present DFT study on crystal and electronic structures of eleven hitherto unknown lead triiodide perovskites with unsaturated three- and four-membered heterocyclic cations containing N, O, and S atoms. According to the calculations, the proposed compounds are semiconductors with direct bandgaps varying in the range [0.84–1.61] eV. Their predicted electronic band structures feature flat bands formed from the heterocycles’ unoccupied π-MOs. With respect to the flat bands’ energies all considered perovskites can be divided into two sets. One set contains compounds whose flat bands are higher in energy than the lowest energy conduction bands formed mainly from unoccupied pi-orbitals of Pb 2+ cations. Another set is comprised of compounds whose flat bands are the lowest energy conduction bands. Compounds described here broaden the family of hybrid metal halide perovskites. All but the lead triiodide containing unstable 2-azirinium cation are suitable for either photovoltaic or optical applications.

AB - We present DFT study on crystal and electronic structures of eleven hitherto unknown lead triiodide perovskites with unsaturated three- and four-membered heterocyclic cations containing N, O, and S atoms. According to the calculations, the proposed compounds are semiconductors with direct bandgaps varying in the range [0.84–1.61] eV. Their predicted electronic band structures feature flat bands formed from the heterocycles’ unoccupied π-MOs. With respect to the flat bands’ energies all considered perovskites can be divided into two sets. One set contains compounds whose flat bands are higher in energy than the lowest energy conduction bands formed mainly from unoccupied pi-orbitals of Pb 2+ cations. Another set is comprised of compounds whose flat bands are the lowest energy conduction bands. Compounds described here broaden the family of hybrid metal halide perovskites. All but the lead triiodide containing unstable 2-azirinium cation are suitable for either photovoltaic or optical applications.

KW - Band structure

KW - DFT

KW - Density of states

KW - Hybrid perovskites

UR - http://www.scopus.com/inward/record.url?scp=85075871017&partnerID=8YFLogxK

U2 - 10.1016/j.jssc.2019.121082

DO - 10.1016/j.jssc.2019.121082

M3 - Article

VL - 282

JO - Journal of solid state chemistry

JF - Journal of solid state chemistry

SN - 0022-4596

M1 - 121082

ER -