Defect-Limited Mobility and Defect Thermochemistry in Mixed A‑Cation Tin Perovskites: (CH3NH3)1–x Cs x SnBr3

• Published in: ACS applied energy materials 2024-09, Vol.7 (18), p.7992-8003
• Main Authors: Asebiah, Dominic Cudjoe, Mozur, Eve M., Koegel, Alexandra A., Nicolson, Adair, Kavanagh, Seán R., Scanlon, David O., Reid, Obadiah G., Neilson, James R.
• Format: Article
• Language: English
• ISSN: 2574-0962; 2574-0962
• DOI: 10.1021/acsaem.4c01708

Hybrid organic–inorganic semiconductors crystallizing in the perovskite structure present a significant opportunity for realizing defect-tolerant semiconductors. In this work, we examine the solid solution, (CH3NH3)1–x Cs x SnBr3, and identify the thermochemistry dictating the intrinsic carrier concentrations and how local structural distortions influences this electronic behavior. This family of compounds exhibits the expected systematic trend in decreasing optical gap with the cesium to methylammonium A-site mixing ratio, x, in the visible region. However, the carrier mobility, as determined from time-resolved microwave conductivity measurements, trends opposite to that expected from first-principles calculations combined with Boltzmann scattering theory calculations of the carrier mobility. We propose that this is a result of increasing carrier scattering with x in (CH3NH3)1–x Cs x SnBr3 due to a significant increase in the carrier density with x. By examining the dependence of the carrier density as a function of x, we infer the compositional-dependence of the average enthalpy and nonconfigurational entropy per defect. While diffraction reveals a cubic aristotypic perovskite structure as a function of x at room temperature, the pair distribution functions obtained from synchrotron X-ray total scattering from these materials are better described by symmetry-adapted displacement modes of the Pm3̅m crystal structure, which we attribute to a large degree of anharmonic dynamics of the atom positions. This analysis shows that CH3NH3 +-rich compositions retain mostly linear Sn–Br–Sn bonding environments through the displacements, while Cs+-rich compositions lead to more significantly bent Sn–Br–Sn environments. We propose that these bent bonding arrangements in Cs-rich compositions yield a higher propensity for defect formation. This also provides a rationale for carrier trapping that gives rise to anomalous microwave transients. Together, these results provide insight into the structure-dynamics-properties relationships in this highly anharmonic system with high amplitude atomic motions and low defect formation energies.