Ligand Size and Chain Length Study of Silver Carboxylates in Focused Electron Beam Induced Deposition

Focused electron beam induced deposition is a versatile tool for the direct fabrication 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, five different silver carboxylates, three fluorinated: [Ag2(µ-O2CCF3)2], [Ag2(µ-O2CC2F5)2], [Ag2(µ-O2CC3F7)2] and two containing hydrogen: [Ag2(µ-O2CCMe2Et)2] and [Ag2(µ-O2CtBu)2] were examined and compared 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 showed high silver content from 42 at.% to above 70at.% and silver nano-crystal formation with impurities of carbon and fluorine incorporated between metal grains. A correlation of the number of carbon atoms in the precursor ligands and silver content of the deposited structures was found. The highest silver contents were achieved for compounds with the shortest CF chains. The deposited silver content depends on the balance of electron induced ligand co-deposition and thermal ligand desorption. Low electron flux is advantageous for high silver content. Our findings demonstrate that silver carboxylates constitute a promising group of precursors for focused electron beam nanoprinting of high silver content materials.