Considering the toxicity of lead ions, substituting Pb with nontoxic elements in halide perovskites, HaPs, has become one of the most significant challenges associated with these materials. Here, we report on replacing Pb with Sn and Ge, focusing on an all-inorganic HaP, CsSn_xGe_1–xBr₃, and using a multihead spray deposition setup for thin-film formation to overcome the low solubility of the precursors and improve film coverage. We find that, in this way, we can form CsSn_xGe_1–xBr₃ films up to high x values as homogeneous solid solutions; i.e., we obtain a range of compositions with one crystal structure (rather than clusters of two phases). The cubic structure of pure CsSnBr₃ is maintained up to 77 atom % Ge, with the lattice spacing decreasing with increasing Ge concentration. The optical band gap is tunable between 1.8 and 2.5 eV, from pure Sn to pure Ge HaP. Most importantly, the perovskite structural stability increases with increasing concentration of Ge, with less oxidation of both Ge and Sn to the +4 state, which can be ascribed to less octahedral tilting and stronger bonding. Electrical and electronic transport measurements show the potential of these materials as Pb-free absorbers for solar cells, particularly, given their band gap range as the top cell of a tandem photovoltaic device.

Hybrid methyl-ammonium lead trihalide perovskites are promising low-cost materials for use in solar cells and other optoelectronic applications. With a certified photovoltaic conversion efficiency record of 20.1%, scale-up for commercial purposes is already underway. However, preparation of large-area perovskite films remains a challenge, and films of perovskites on large electrodes suffer from non-uniform performance. Thus, production and characterization of the lateral uniformity of large-area films is a crucial step towards scale-up of devices. In this paper, we present a reproducible method for improving the lateral uniformity and performance of large-area perovskite solar cells (32 cm²). The method is based on methyl-ammonium iodide (MAI) vapor treatment as a new step in the sequential deposition of perovskite films. Following the MAI vapor treatment, we used high throughput techniques to map the photovoltaic performance throughout the large-area device. The lateral uniformity and performance of all photovoltaic parameters (V_oc, J_sc, Fill Factor, Photo-conversion efficiency) increased, with an overall improved photo-conversion efficiency of ∼100% following a vapor treatment at 140 °C. Based on XRD and photoluminescence measurements, We propose that the MAI treatment promotes a “healing effect” to the perovskite film which increases the lateral uniformity across the large-area solar cell. Thus, the straightforward MAI vapor treatment is highly beneficial for large scale commercialization of perovskite solar cells, regardless of the specific deposition method.

We report continuous wave laser-assisted evaporation (CLE), a thin film deposition technique that yields phase-pure and stoichiometric thin films of halide perovskites (HaPs) from stoichiometric HaP targets. We use methylammonium lead bromide (MAPbBr3) to demonstrate the ability to grow with CLE well-oriented and smooth thin films on various substrates. Further, we show the broader applicability of CLE by preparing films of several other 3D HaP compounds, viz., methylammonium lead iodide, formamidinium lead bromide, and a 2D one, butylammonium lead iodide. CLE is a single-source, solvent-free, room-temperature process that needs only roughing pump vacuum; it allows the deposition of hybrid organic-inorganic compound films without needing post-thermal treatment or an additional organic precursor source to yield the intended product. The resulting films are polycrystalline and highly oriented. All these features, and the fact that one stoichiometric source serves as the target, make for an attractive, potentially scalable dry deposition approach.