Temperature-Dependent Local Electrical Properties of Organic–Inorganic Halide Perovskites: In Situ KPFM and c-AFM Investigation

Organic–inorganic halide perovskite materials are emerging as a new class of photoelectric materials for its low cost, easy preparation, and, especially, outstanding optoelectronic properties. Although tremendous efforts have been made on the regulation and optimization of perovskite materials and their microscopic electrical properties for high-efficiency solar cells, few reports focus on the evolution of electrical properties with temperature changes, especially at the microscopic scale, which will directly affect the device performances at varying temperatures. Here, we map the contact potential difference and photocurrent distribution of MAPbI3 at different temperatures in situ by Kelvin probe force microscopy and conductive atomic force microscopy, emphasizing the different influences of variable temperature and phase transition on the photoelectric properties of grains and grain boundaries (GBs). It is discovered that both the Fermi level and photocurrent decrease as the sample is heated from 30 to 80 °C gradually because of the variation of effective carrier concentration and the degradation of carrier mobility implicated by lattice vibration scattering. The difference between the Fermi level at GBs and that on the grains ascends first and then descends, peaking at 50 °C, near which MAPbI3 transforms from a tetragonal phase to a cubic phase. This peak is speculated as a comprehensive consequence of the increasing difference of the Fermi level of semiconductors with different doping concentrations and the converging properties of grains and GBs with the temperature rising because the lower ion activation energy of the cubic phase at higher temperatures facilitates greatly the ions' movement between grains and GB. The variation trend of the difference of the photocurrent is the same. These findings advance the knowledge on the temperature-induced variations of microscopic photoelectrical properties of organic–inorganic hybrid perovskite materials, which may guide the development of strategies for improving their thermal stability.