Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites: Replacement of lead with alkaline-earth metals

Abstract

Organic and inorganic lead halogen perovskites, and in particular, $\mathrm{C}{\mathrm{H}}_{3}\mathrm{N}{\mathrm{H}}_{3}\mathrm{Pb}{\mathrm{I}}_{3}$, have during the last years emerged as a class of highly efficient solar cell materials. Herein we introduce metalorganic halogen perovskite materials for energy-relevant applications based on alkaline-earth metals. Based on the classical notion of Goldschmidt's rules and quantum mechanical considerations, the three alkaline-earth metals, Ca, Sr, and Ba, are shown to be able to exchange lead in the perovskite structure. The three alkaline-earth perovskites, $\mathrm{C}{\mathrm{H}}_{3}\mathrm{N}{\mathrm{H}}_{3}\mathrm{Ca}{\mathrm{I}}_{3},\mathrm{C}{\mathrm{H}}_{3}\mathrm{N}{\mathrm{H}}_{3}\mathrm{Sr}{\mathrm{I}}_{3}$, and $\mathrm{C}{\mathrm{H}}_{3}\mathrm{N}{\mathrm{H}}_{3}\mathrm{Ba}{\mathrm{I}}_{3}$, as well as the reference compound, $\mathrm{C}{\mathrm{H}}_{3}\mathrm{N}{\mathrm{H}}_{3}\mathrm{Pb}{\mathrm{I}}_{3}$, are in this paper investigated with density functional theory (DFT) calculations, which predict these compounds to exist as stable perovskite materials, and their electronic properties are explored. A detailed analysis of the projected molecular orbital density of states and electronic band structure from DFT calculations were used for interpretation of the band-gap variations in these materials and for estimation of the effective masses of the electrons and holes. Neglecting spin-orbit effects, the band gap of $\mathrm{MACa}{\mathrm{I}}_{3},\mathrm{MASr}{\mathrm{I}}_{3}$, and $\mathrm{MABa}{\mathrm{I}}_{3}$ were estimated to be 2.95, 3.6, and 3.3 eV, respectively, showing the relative change expected for metal cation exchange. The shifts in the conduction band (CB) edges for the alkaline-earth perovskites were quantified using scalar relativistic DFT calculations and tight-binding analysis, and were compared to the situation in the more extensively studied lead halide perovskite, $\mathrm{C}{\mathrm{H}}_{3}\mathrm{N}{\mathrm{H}}_{3}\mathrm{Pb}{\mathrm{I}}_{3}$, where the change in the work function of the metal is the single most important factor in tuning the CB edge and band gap. The results show that alkaline-earth-based organometallic perovskites will not work as an efficient light absorber in photovoltaic applications but instead could be applicable as charge-selective contact materials. The rather high CB edge and the wide band gap together with the large difference of the electron and hole effective masses make them good candidates for $n$-type selective layers in hot carrier injection solar cell devices together with some light absorber candidates. The fact that they have similar lattice constants as the lead perovskite and suitable positions of the valence band edges open up the possibility to use them also as thin epitaxial $p$-type hole selective contacts in combination with the lead halogen perovskite materials. This can lead to both charge selectivity as well as to superior crystal growth of lead perovskite with less contact stress, which is interesting for further investigations.