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Mixed halide perovskites can provide optimal bandgaps for tandem solar cells which are key to improved cost-efficiencies, but can still suffer from detrimental illumination-induced phase segregation. Here we employ optical-pump terahertz-probe spectroscopy to investigate the impact of halide segregation on the charge-carrier dynamics and transport properties of mixed halide perovskite films. We reveal that, surprisingly, halide segregation results in negligible impact to the THz charge-carrier mobilities, and that charge carriers within the I-rich phase are not strongly localised. We further demonstrate enhanced lattice anharmonicity in the segregated I-rich domains, which is likely to support ionic migration. These phonon anharmonicity effects also serve as evidence of a remarkably fast, picosecond charge funnelling into the narrow-bandgap I-rich domains. Our analysis demonstrates how minimal structural transformations during phase segregation have a dramatic effect on the charge-carrier dynamics as a result of charge funnelling. We suggest that because such enhanced recombination is radiative, performance losses may be mitigated by deployment of careful light management strategies in solar cells. Phase segregation in mixed halide perovskite is known to alter the optoelectronic properties, but how it affects charge carriers is not clear. Here, the authors use THz spectroscopy to reveal that high carrier mobilities are well preserved, while recombination dynamics is affected by charge funnelling upon segregation. [ABSTRACT FROM AUTHOR]

Trap‐related charge‐carrier recombination fundamentally limits the performance of perovskite solar cells and other optoelectronic devices. While improved fabrication and passivation techniques have reduced trap densities, the properties of trap states and their impact on the charge‐carrier dynamics in metal‐halide perovskites are still under debate. Here, a unified model is presented of the radiative and nonradiative recombination channels in a mixed formamidinium‐cesium lead iodide perovskite, including charge‐carrier trapping, de‐trapping and accumulation, as well as higher‐order recombination mechanisms. A fast initial photoluminescence (PL) decay component observed after pulsed photogeneration is demonstrated to result from rapid localization of free charge carriers in unoccupied trap states, which may be followed by de‐trapping, or nonradiative recombination with free carriers of opposite charge. Such initial decay components are shown to be highly sensitive to remnant charge carriers that accumulate in traps under pulsed‐laser excitation, with partial trap occupation masking the trap density actually present in the material. Finally, such modelling reveals a change in trap density at the phase transition, and disentangles the radiative and nonradiative charge recombination channels present in FA0.95Cs0.05PbI3, accurately predicting the experimentally recorded PL efficiencies between 50 and 295 K, and demonstrating that bimolecular recombination is a fully radiative process. [ABSTRACT FROM AUTHOR]

Hybrid metal-halide perovskites are promising new materials for use in solar cells; however, their chemical stability in the presence of moisture remains a significant drawback. Quasi two-dimensional (2D) perovskites that incorporate hydrophobic organic interlayers offer improved resistance to degradation by moisture, currently still at the cost of overall cell efficiency. To elucidate the factors affecting the optoelectronic properties of these materials, we have investigated the charge transport properties and crystallographic orientation of mixed methylammonium (MA)-phenylethylammonium (PEA) lead iodide thin films as a function of the MA-to-PEA ratio and, thus, the thickness of the "encapsulated" MA lead-halide layers. We find that monomolecular charge-carrier recombination rates first decrease with increasing PEA fraction, most likely as a result of trap passivation, but then increase significantly as excitonic effects begin to dominate for thin confined layers. Bimolecular and Auger recombination rate constants are found to be sensitive to changes in electronic confinement, which alters the density of states for electronic transitions. We demonstrate that effective charge-carrier mobilities remain remarkably high (near 10 cm²V−1s−1) for intermediate PEA content and are enhanced for preferential orientation of the conducting lead iodide layers along the probing electric field. The trade-off between trap reduction, electronic confinement, and layer orientation leads to calculated charge-carrier diffusion lengths reaching a maximum of 2.5 μm for intermediate PEA content (50%). [ABSTRACT FROM AUTHOR]