Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3

Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb–I bonds. The comparison of surface energies for the most stable configurations identified for all surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms, which are directly correlated with the number of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as a first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to help facilitate further breakthroughs in solar conversion efficiencies.