Hybrid organic-inorganic perovskites (PVKs) offer exceptional optoelectronic performance, yet reproducible and scalable co-evaporation remains challenging. This study examines the interplay of factors affecting compositional control during three-source PVK deposition. We identify chamber pressure, precursor cross-contamination, and flux instability – especially from organic salts such as formamidinium iodide (FAI) – as major sources of variability. A critical influence is the occurrence of cross-reading, where omnidirectional evaporation of FAI contributes to the reading on the quartz crystal microbalance (QCM) sensors monitoring the inorganic precursors like caesium bromide (CsBr) and lead iodide (PbI₂) even though shielding is present. This effect, strongly dependent on FAI load, deposition rate, and QCM sensor position, erroneously inflates measured fluxes, leading to inaccurate rate control and unintentional compositional drift. Maintaining A-, B- and X-site stoichiometry therefore requires dynamic adjustment of precursor rates, particularly at higher deposition speeds where mean free path limitations come into play. We demonstrate the successful deposition of perovskite layers at a deposition speed of 27.8 nm min⁻¹ as the practical ceiling for the investigated Cs_xFA_1-xPb(I_1-xBr_x)₃ composition within our experimental framework. These findings highlight the delicate balance between deposition speed, precursor stability, and film quality, underscoring the need for improved delivery systems - such as continuous precursor feedthrough, multiple organic sources, alternative vapor transport or flash evaporation methods – to achieve reproducible, fast and large-scale fabrication of high-performance PVK films.

Sequential thermal evaporation is an emerging technique for obtaining perovskite (PVK) photoactive materials for solar cell applications. Advantages include solvent-free processing, accurate stoichiometry control, and scalable processing. Nevertheless, the power conversion efficiency (PCE) of PVK solar cells (PSCs) fabricated by evaporation still lags behind that of solution-processed PSCs. Here, based on multi-cycle sequential thermal evaporation, we systematically investigate the effects of the post-deposition annealing temperature on the PVK properties in terms of surface morphology, opto-electronic properties, and device performance. We find that the average grain size increases to almost 1 μm and charge carrier mobilities exceed 50 cm2 V−1 s−1 when the annealing temperature is increased to 170 °C. We introduce a trace of PbCl2 to the multi-cycle sequential deposition to improve the absorber crystallinity at a lower annealing temperature of 150 °C, as evidenced by the XRD and PL analyses. The resulting PSC in a p–i–n structure yields a PCE of 18.5% with a cell area of 0.09 cm2. With the same deposition parameters, the cell area is scaled up to 0.36 cm2, achieving champion PCEs of 17.06%. This indicates the great potential of this technology for the commercialization of PSCs in the future.

To boost the efficiency of perovskite solar cells beyond the limit of a single-junction cell, tandem cells are employed, requiring low bandgap materials. This is realized by partially substituting lead(II) (Pb2+) with tin(II) (Sn2+) in the perovskite structure. In this work, a scalable method is presented to produce formamidinium lead tin iodide (FAPb0.5Sn0.5I3) films by sequential thermal evaporation (sTE) of PbSnI4, which is an alloy of SnI2 and PbI2, and FAI, in vacuum. Annealing at 200 °C yields a highly oriented and crystalline layer comprising grains over 1 µm on average. Photoconductance measurements reveal carrier lifetimes exceeding 2 µs and mobilities ≈100 cm2/(Vs). Structural analysis confirms that, while interdiffusion is abundant even at room temperature, the complete conversion requires high temperatures. Although the incorporation of Cs+ into the A-site of the perovskite increases the grain size, charge carrier dynamics are reduced. A comparison between the sTE films and spin-coated samples of the same composition demonstrates the superior photoconductance of the sTE films, without the need for any additives. Overall, this study showcases the potential of sTE for producing high-quality low band gap (LBG) perovskite materials.