Effect of Precursor Composition on Ion Migration in Hybrid Perovskite CH₃NH₃PbI₃

Abstract

We used thin-film transistors (TFTs) to understand the effect of precursor composition on ion migration in the hybrid perovskite CH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> NH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> PbI <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> (MAPbI <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> ). For all the precursor compositions we investigated (i.e. MAI/PbI <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> ratios of 0.5, 0.8, 1.0, and 1.2), the TFTs exhibited anomalous hysteresis in their current-voltage (I-V) characteristics, indicating mixed ionic-electronic conduction. The hysteresis in the TFTs with MAI/PbI <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> = 0.5 was the largest, followed by that of the TFTs with ratios of 1.2, 1.0, and 0.8. Although residual PbI <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> was the source of hysteresis in the PbI <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> -rich TFTs (MAI/PbI <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> = 0.5), we conclude that it may enhance electronic conduction and minimize ion migration when present in small amounts (as in the case of MAI/PbI <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> = 0.8). Ion vacancy defects in grain boundaries are pathways for ion migration and the PbI <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> residues passivate these defects, there by minimizing the vacancy-mediated migration of ions in the MAPbI <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> .