Charge‐Carrier Dynamics, Mobilities, and Diffusion Lengths of 2D–3D Hybrid Butylammonium–Cesium–Formamidinium Lead Halide Perovskites

Perovskite solar cells (PSCs) have improved dramatically over the past decade, increasing in efficiency and gradually overcoming hurdles of temperature‐ and humidity‐induced instability. Materials that combine high charge‐carrier lifetimes and mobilities, strong absorption, and good crystallinity of 3D perovskites with the hydrophobic properties of 2D perovskites have become particularly promising candidates for use in solar cells. In order to fully understand the optoelectronic properties of these 2D–3D hybrid systems, the hybrid perovskite BAx(FA0.83Cs0.17)1‐xPb(I0.6Br0.4)3 is investigated across the composition range 0 ≤ x ≤ 0.8. Small amounts of butylammonium (BA) are found that help to improve crystallinity and appear to passivate grain boundaries, thus reducing trap‐mediated charge‐carrier recombination and enhancing charge‐carrier mobilities. Excessive amounts of BA lead to poor crystallinity and inhomogeneous film formation, greatly reducing effective charge‐carrier mobility. For low amounts of BA, the benevolent effects of reduced recombination and enhanced mobilities lead to charge‐carrier diffusion lengths up to 7.7 µm for x = 0.167. These measurements pave the way for highly efficient, highly stable PSCs and other optoelectronic devices based on 2D–3D hybrid materials. Optoelectronic properties, including charge‐carrier dynamics and mobilities, are examined for a broad compositional range of hybrid perovskites containing 2D layered material at the boundaries of 3D perovskites grains. An optimal composition range is demonstrated that allows for good environmental stability, effective trap passivation, and efficient charge transport, making these hybrid 2D–3D materials ideal for photovoltaic and optoelectronic devices.