The dual-source vacuum deposition of 2D perovskite films of the type PEA₂PbX₄, (PEA = phenethylammonium and X = I^-, Br^-, or a combination of both) is presented. Low-temperature deposited 2D perovskite films showed high crystallinity with the expected trend of bandgap as a function of halide type and concentration. Importantly, we observed an unavoidable halide cross-contamination among different deposition runs, as well as a strong dependence of the material quality on the type of halide precursors used. These findings should be taken into account in the development of vacuum processing for low-dimensional mixed halide perovskites.

Herein we demonstrate the dry synthesis of CsBi3I10 both as a free-standing material and in the form of homogeneous thin films, deposited by thermal vacuum deposition. Chemical and optical characterization shows high thermal stability, phase purity, and photoluminescence centered at 700 nm, corresponding to a bandgap of 1.77 eV. These characteristics make CsBi3I10 a promising low-toxicity material for wide bandgap photovoltaics. Nevertheless, the performance of this material as a semiconductor in solar cells remains rather limited, which can be at least partially ascribed to a low charge carrier mobility, as determined from pulsed-radiolysis time-resolved microwave conductivity. Further developments should focus on understanding and overcoming the current limitations in charge mobility, possibly by compositional tuning through doping and/or alloying, as well as optimizing the thin film morphology which may be another limiting factor. This journal is

Phase-pure CsSnI₃, FASnI₃, Cs(PbSn)I₃, FA(PbSn)I₃ perovskites (FA = formamidinium = HC(NH₂)₂ ⁺) as well as the analogous so-called vacancy-ordered double perovskites Cs₂SnI₆ and FA₂SnI₆ are mechanochemically synthesized. The addition of SnF₂ is found to be crucial for the synthesis of Cs-containing perovskites but unnecessary for hybrid ones. All compounds show an absorption onset in the near-infrared (NIR) region, which makes them especially relevant for photovoltaic applications. The addition of Pb(II) and SnF₂ is crucial to improve the electronic properties in 3D Sn(II)-based perovskites, in particular their charge carriers mobility (≈0.2 cm² Vs⁻¹) which is enhanced upon reduction of the dark carrier conductivity. Stokes-shifted photoluminescence is observed on dry powders of Sn(II)-based perovskites, which makes these materials promising for light-emitting and sensing applications. Thermal stability of all compounds is examined, revealing no significant degradation up to at least 200 °C. This meets the requirements for standard operation conditions of most optoelectronic devices and is potentially compatible with thermal vacuum deposition of polycrystalline thin films.

Low-dimensional (quasi-) 2D perovskites are being extensively studied in order to enhance the stability and the open-circuit voltage of perovskite solar cells. Up to now, thin 2D perovskite layers on the surface and/or at the grain boundaries of 3D perovskites have been deposited solely by solution processing, leading to unavoidable intermixing between the two phases. In this work, we report the fabrication of 2D/3D/2D perovskite heterostructures by dual-source vacuum deposition, with the aim of studying the interaction between the 3D and 2D phases as well as the charge transport properties of 2D perovskites in neat 2D/3D interfaces. Unlike what is normally observed in solution-processed 3D/2D systems, we found a reduced charge transport with no direct evidence of surface passivation, in spite of larger open-circuit voltage. This is likely due to a nonfavorable orientation of the 2D perovskite with respect to methylammonium lead iodide and to the formation of 2D phases with very low dimensionality (pure 2D).