Influence of Halide Substitution and External Stimuli on Ion Transport in Inverted MAPb(I1-xBrx)3 Perovskite Solar Cells

The coupled electronic-ionic response in various MAPb(I1-xBrx)3-based inverted perovskite solar cells (PSCs) is studied in-operando by impedance spectroscopy (IS) under varied AM1.5G light intensities and electrical biases. We show that the concentration of Br- in the composition significantly alters the capacitance and resistive response of the PSC under external stimuli. For example, we observed that the low frequency capacitance does not increase proportionally with light intensity, instead it is highly dependent on the amount of Br- in the composition. We found that the recombination resistance (Rrec) has a linear inverse relationship with light intensity in MAPbI3 and MAPbBr3 whereas, the mixed compositions show deviation. Interestingly, the deviation of Rrec from linearity also scales with the increase in Br- concentration. Upon applying an electrical bias, a large deviation of Rrec from linearity was observed all mixed halide compositions exhibited a non-linear inverse trend. We further report the diffusion coefficient (D) for each MAPb(I1-xBrx)3 composition under different light intensity. Notably, the D values decreased on changing the composition from MAPbI3 (10-7 cm2 s-1) to MAPb(I0.8Br0.2)3 and MAPbBr3 (10-8 cm2 s-1). On the other hand, mixed compositions containing more than 20% Br- concentration show faster diffusion kinetics. Overall, our results emphasize on the complex and intertwined nature of electronic and ionic response in PSC that is tunable by changing the halide composition.