Understanding the impact of environmental gaseous on the surface of organometal halide perovskites (OMHPs) couples to the electronic and ionic transport is critically important. Here, we explore the transport behavior and origins of the gas sensitivity in MAPbBr3 single crystals (SCs) devices using impedance spectroscopy and current relaxation measurements. Strong resistive response occurs when crystals are exposed to different environments. It was shown that SC response to the environment is extremely different at the surface as compared to the bulk due to the disorder surface chemistry. The nonlinear transport properties studied using ultrafast Kelvin probe force microscopy (G-KPFM) to unravel spatio-temporal charge dynamics at SC/electrode interface. The relaxation processes observed in pulse relaxation and G-KPFM measurements along with gas sensitivity of crystals suggest the presence of a triple-phase boundary between environment, electrode, and crystal. Results indicate that the environment is a nontrivial component in the operation of OMHP devices which is reminiscent of fuel cell systems. Furthermore, the triple-phase boundary can play a significant role in the transport properties of OMHPs due to the possibility of the redox processes coupled to the concentration of bulk ionic species. Although instrumental for understanding the device characteristics of perovskites, our studies suggest a new opportunity of coupling the redox chemistry of the Br2-Br- pair that defines the bulk ionic conductivity of MAPbBr3 with the redox chemistry of gaseous (or liquid) environment via a suitable electrocatalytic system to enable new class of energy storage devices and gas sensors.
Keywords: charge transport; electrode; environment; organometal halide perovskite; redox; relaxation time.