New Pb-Free Stable Sn–Ge Solid Solution Halide Perovskites Fabricated by Spray Deposition

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, CsSnxGe1-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 CsSnxGe1-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.