The effect of the orientation of the cation MA (i.e., CH3NH3) on the physical properties of MAPbI3 are investigated using the density functional theory. We report that the Fermi energy level exhibits a large variation with MA orientation, and it is this Fermi level variation that makes this material unique and so different from the non-organic perovskites. The Fermi level variation with orientation of MA is proposed to be responsible for the experimentally observed intrinsic open-circuit voltage V_OC, ambipolarity, and long lifetime of the excitons. Based on our results, ferroelectric domains in the low-temperature orthorhombic phase or clusters of MA molecules not rotating in unison (as a consequence of e.g. impurities and/or defects) in the higher-temperature tetragonal and cubic phases are proposed to be responsible for ambipolarity. This is because any given two adjacent domains or clusters with different MA s average orientations may have very different Fermi levels, causing them to behave as an effective diode. Also, the measured significant lifetime of excitons in MAPbI3 finds a natural explanation using this effective diode. Thus, our work provides a unified manner for explaining at least these three important properties in terms of the rotation-induced Fermi level variations. We used the density functional theory to get our results.
Spin dynamics of excitons and carriers in mixed-cation MA$_{x}$FA$_{1-x}$PbI$_{3}$ perovskite crystals: alloy fluctuations probed by optical orientation
Empa-Swiss Federal Laboratories for Materials Science and Technology（瑞士联邦材料科技研究所）
Electronic and optical properties of the fully and partially inverse CoFe$_{2}$O$_{4}$ spinel from first principles calculations including many-body effects
