| Summary: | Gas-assisted focused electron-beam-induced deposition is a versatile tool for the direct writing of complex-shaped nanostructures with unprecedented shape fidelity and resolution. While the technique is well-established for various materials, the direct electron beam writing of silver is still in its infancy. Here, we examine and compare five different silver carboxylates, three perfluorinated: [Ag<sub>2</sub>(µ-O<sub>2</sub>CCF<sub>3</sub>)<sub>2</sub>], [Ag<sub>2</sub>(µ-O<sub>2</sub>CC<sub>2</sub>F<sub>5</sub>)<sub>2</sub>], and [Ag<sub>2</sub>(µ-O<sub>2</sub>CC<sub>3</sub>F<sub>7</sub>)<sub>2</sub>], and two containing branched substituents: [Ag<sub>2</sub>(µ-O<sub>2</sub>CCMe<sub>2</sub>Et)<sub>2</sub>] and [Ag<sub>2</sub>(µ-O<sub>2</sub>C<sup>t</sup>Bu)<sub>2</sub>], as potential precursors for focused electron-beam-induced deposition. All of the compounds show high sensitivity to electron dissociation and efficient dissociation of Ag-O bonds. The as-deposited materials have silver contents from 42 at.% to above 70 at.% and are composed of silver nano-crystals with impurities of carbon and fluorine between them. Precursors with the shortest carbon-fluorine chain ligands yield the highest silver contents. In addition, the deposited silver content depends on the balance of electron-induced ligand co-deposition and ligand desorption. For all of the tested compounds, low electron flux was related to high silver content. Our findings demonstrate that silver carboxylates constitute a promising group of precursors for gas-assisted focused electron beam writing of high silver content materials.
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