Metal halide perovskites have unique optical and electrical properties, which make them an excellent class of materials for a broad spectrum of optoelectronic applications. However, it is with photovoltaic devices that this class of materials has reached the apotheosis of popularity. High power conversion efficiencies are achieved with lead‐based compounds, which are toxic to the environment. Tin‐based perovskites are the most promising alternative because of their bandgap close to the optimal value for photovoltaic applications, the strong optical absorption, and good charge carrier mobilities. Nevertheless, the low defect tolerance, the fast crystallization, and the oxidative instability of tin halide perovskites currently limit their efficiency. The aim of this review is to give a detailed overview of the crystallographic, photophysical, and optoelectronic properties of tin‐based perovskite compounds in their multiple forms from 3D to low‐dimensional structures. At the end, recent progress in tin‐based perovskite solar cells are reviewed, mainly focusing on the detail of the strategies adopted to improve the device performances. For each subtopic, the current challenges and the outlook are discussed, with the aim to stimulate the community to address the most important issues in a concerted manner.

2D perovskites offers a rich playing field to explore exciton physics and they possess a great potential for a variety of opto-electronic applications. Whilst their photophysics shows intricate interactions of excitons with the lattice, most reports have so far relied on single compound studies. With the exception of variations of the organic spacer cations, the effect of constituent substitution on the photophysics and the nature of emitting species, in particular, have remained largely under-explored. Here PEA 2 PbBr 4 , PEA 2 PbI 4 , and PEA 2 SnI 4 (where PEA stands for phenylethylammonoium) are studied through a variety of optical spectroscopy techniques to reveal a complex set of excitonic transitions at low temperature. Weak high-energy features are attributed to vibronic transitions breaking Kasha's, for which the responsible phonons cannot be accessed through simple Raman spectroscopy. Bright peaks at lower energy are due to two distinct electronic states, of which the upper is a convolution of the free exciton and a localized dark state and the lower is attributed to recombination involving shallow defects. This study offers deeper insights into the photophysics of 2D perovskites through compositional substitution and highlights critical limits to the communities' current understanding of processes in these compounds.

2D metal halide perovskites can show narrow and broad emission bands (BEs), and the latter's origin is hotly debated. A widespread opinion assigns BEs to the recombination of intrinsic selftrapped excitons (STEs), whereas recent studies indicate they can have an extrinsic defect-related origin. Here, we carry out a combined experimental−computational study into the microscopic origin of BEs for a series of prototypical phenylethylammonium-based 2D perovskites, comprising different metals (Pb, Sn) and halides (I, Br, Cl). Photoluminescence spectroscopy reveals that all of the compounds exhibit BEs. Where not observable at room temperature, the BE signature emerges upon cooling. By means of DFT calculations, we demonstrate that emission from halide vacancies is compatible with the experimentally observed features. Emission from STEs may only contribute to the BE in the wide-band-gap Br-and Cl-based compounds. Our work paves the way toward a complete understanding of broad emission bands in halide perovskites that will facilitate the fabrication of efficient narrow and white light emitting devices.

To date, there are no reports of 3D tin perovskite being used as a semiconducting channel in field‐effect transistors (FETs). This is probably due to the large amount of trap states and high p‐doping typical of this material. Here, the first top‐gate bottom‐contact FET using formamidinium tin triiodide perovskite films is reported as a semiconducting channel. These FET devices show a hole mobility of up to 0.21 cm2 V−1 s−1, an ION/OFF ratio of 104, and a relatively small threshold voltage (VTH) of 2.8 V. Besides the device geometry, the key factor explaining this performance is the reduced doping level of the active layer. In fact, by adding a small amount of the 2D material in the 3D tin perovskite, the crystallinity of FASnI3 is enhanced, and the trap density and hole carrier density are reduced by one order of magnitude. Importantly, these transistors show enhanced parameters after 20 months of storage in a N2 atmosphere.

Low bandgap lead‐tin halide perovskites are predicted to be candidates to maximize the performance of single junction and tandem solar cells based on metal halide perovskites. In spite of the tremendous progress in lab‐scale device efficiency, devices fabricated with scalable techniques fail to reach the same efficiencies, which hinder their potential industrialization. Herein, a method is proposed that involves a template of a 2D perovskite deposited with a scalable technique (blade coating), which is then converted in situ to form a highly crystalline 3D lead‐tin perovskite. These templated grown films are alloyed with stoichiometric ratio and are highly oriented with the (l00) planes aligning parallel to the substrate. The low surface/volume ratio of the obtained single‐crystal‐like films contributes to their enhanced stability in different environments. Finally, the converted films are demonstrated as active layer for solar cells, opening up the opportunity to develop this scalable technique for the growth of highly crystalline hybrid halide perovskites for photovoltaic devices.