Ge₁₄Br₈(PⁿPr₃)₄: A Material for Laser-Induced Printing of Elemental Germanium

The continued miniaturization of microelectronic systems requires new strategies for fabricating microelectronic materials beyond conventional lithography and metal evaporation. Metalloid nanoclusters offer promising alternatives for printing and patterning conductive and semiconductive elements. Here, we report on the synthesis, structural characterization, and first application of the soluble metalloid germanium cluster Ge₁₄Br₈(PⁿPr₃)₄, obtained via controlled disproportionation of a metastable GeBr solution. Substitution of the phosphine ligands markedly enhances the solubility in organic solvents, enabling comprehensive spectroscopic characterization via nuclear magnetic resonance (NMR), ultraviolet-visible (UV-vis), and mass spectrometry. Furthermore, the cluster demonstrates a high Ge content of 45 wt %, rendering it a possible precursor for laser-induced writing of elemental germanium under inert conditions. To demonstrate its potential, we fabricate deliberately designed patterns of Ge microstructures and assess their semiconducting behavior. This work establishes the first example of direct laser writing of germanium from a soluble metalloid cluster precursor, opening new pathways for additive microfabrication in semiconductor technology.