Lead‐Free Semiconductors: Soft Chemistry, Dimensionality Control, and Manganese‐Doping of Germanium Halide Perovskites
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Lead halide perovskites have drawn enormous interest due to their exceptional photovoltaic and optoelectronic properties. However, the heavy metal lead is harmful to humans and the environment resulting in a need for strategies to replace this toxic element. Herein, we report a facile aqueous synthesis of CsGeX3 (X=I, Br) perovskite nanocrystals with size control achieved by varying the concentration of a cysteammonium halide ligand. We observe a variety of morphologies including pyramidal, hexagonal, and spheroidal. CsGeX3 nanocrystals undergo a lattice expansion due to partial replacement of Cs+ with larger cysteNH3+ cations into their lattice. We successfully dope Mn2+into the CsGeX3 lattice for the first time with incorporation of up to 29% in bulk and 16% in nano samples. XRD peak shifts and EPR hyperfine splitting strongly indicate that Mn2+ is doped into the lattice. Our results introduce a new member to the lead‐free halide perovskite family and set the fundamental stage for their use in optoelectronic devices.