Hybrid halide perovskites are emerging semiconducting materials, with a diverse set of remarkable optoelectronic properties. Besides the widely studied three-dimensional (3D) perovskites, two-dimensional (2D) perovskites show significant potential as photovoltaic (PV) active layers while exhibiting high moisture resistance. Here, we report two series of new 2D halide perovskite solid solutions: (HA)Pb1–xSnxI4 and (BZA)2Pb1–xSnxI4 (x = 1, 0.75, 0.5, 0.25, 0), where HA stands for the organic spacer histammonium and BZA stands for benzylammonium cations. These compounds are assembled by corner-sharing octahedral [MI6]4– units stabilizing single-layered, anionic, inorganic perovskite sheets with organic cations filled in between. The optical band gaps are heavily affected by the M–I–M perovksite angles with the band gap steadily decreasing when the angle approaches 180°, ranging from 2.18 eV for (BZA)2PbI4 to 2.05 eV for (HA)PbI4. We find an anomalous trend in electronic band gap in the mixed compositions (HA)Pb1–xSnxI4 and (BZA)2Pb1–xSnxI4. When Sn substitutes for Pb to form a solid solution, the band gap further decreases to 1.67 eV for (HA)SnI4. The minimum band gap is at x = 0.75 at 1.74 eV. For BZA, the irregular trend is more intense, as all the intermediate compounds (BZA)2Pb1–xSnxI4 (x = 0.75, 0.5, 0.25) have even slightly lower band gaps than (BZA)2SnI4 (1.89 eV). DFT calculations confirm the pure Pb and Sn compounds are direct band gap semiconductors. Relatively shorter photoluminescence (PL) lifetime in (BZA)2PbI4 than (HA)PbI4 is observed, suggesting faster recombination rates of the carriers. Solution deposited thin films of (HA)PbI4 and (BZA)2PbI4 show drastically different orientations with (HA)PbI4 displaying a perpendicular rather than parallel growth orientation with respect to the substrate, which is more favorable for PV devices. The higher potential in PV applications of the HA system is indicated by device performance, as the champion air stable planar device with the structure ITO/PEDOT:PSS/2D-perovskite/PCBM/Al of (HA)PbI4 achieves a preliminary power conversion efficiency (PCE) of 1.13%, featuring an open-circuit voltage (VOC) of 0.91 V.

Role of Organic Counterion in Lead- and Tin-Based Two-Dimensional Semiconducting Iodide Perovskites and Application in Planar Solar Cells