Interplay of spin-orbit coupling and lattice distortion in metal substituted 3D tri-chloride hybrid perovskites

Claudine Katan (1) , Laurent Pedesseau (2) , Mikaël Kepenekian (1) , Alain Rolland (2) , Jacky Even (2)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 FOTON - Fonctions Optiques pour les Technologies de l'informatiON

Within the scope of this ‘Perovskite Solar Cells’ themed issue, following their rise to superstardom for photovoltaics, we herein begin by recalling a couple of pioneering works and basic concepts useful to rationalize structure-property relationships and already gained by several decades of active research on hybrid perovskite materials. Effects of band folding and octahedral tilting related to structural phase transitions are given particular emphasis. Next, we investigate theoretically metal substitution based on available crystallographic data of the tri-chloride CH3NH3MCl3 (M=Pb, Sn, Ge) crystal structures, having a 3D inorganic network of corner-shared octahedra. In fact, both the chlorine-based hybrid perovskites and metal substitution have not received much attention from materials science theoreticians. Moreover, metal substitution leads to additional crystal structure diversity with formation of pyramidal MCl3- ions. Distinct focus is paid to their optoelectronic properties, especially band-gap and absorption. Moreover, investigation of bromides and iodides analogues reveals that spin-orbit interaction stemming from halogens may also be significant, especially for iodine. This can be analysed from the atomic charges calculated through the Atom In Molecules (AIM) quantum theory.

Mots clés: hybrid perovskite; spin-orbit coupling; DFT; band-gap

Domaines: Chimie théorique et/ou physique

Claudine Katan, Laurent Pedesseau, Mikaël Kepenekian, Alain Rolland, Jacky Even. Interplay of spin-orbit coupling and lattice distortion in metal substituted 3D tri-chloride hybrid perovskites. Journal of Materials Chemistry A, 2015, 3, pp.9232-9240. ⟨10.1039/C4TA06418F⟩. ⟨hal-01103517v1⟩