Vanadium and Manganese Carbonyls as Precursors in Electron-Induced and Thermal Deposition Processes

The material composition and electrical properties of nanostructures obtained from focused electron beam-induced deposition (FEBID) using manganese and vanadium carbonyl precursors have been investigated. The composition of the FEBID deposits has been compared with thin films derived by the thermal decomposition of the same precursors in chemical vapor deposition (CVD). FEBID of V(CO)₆ gives access to a material with a V/C ratio of 0.63-0.86, while in CVD a lower carbon content with V/C ratios of 1.1-1.3 is obtained. Microstructural characterization reveals for V-based materials derived from both deposition techniques crystallites of a cubic phase that can be associated with VC_1-xO_x. In addition, the electrical transport measurements of direct-write VC_1-xO_x show moderate resistivity values of 0.8-1.2 × 10³ µΩ·cm, a negligible influence of contact resistances and signatures of a granular metal in the temperature-dependent conductivity. Mn-based deposits obtained from Mn₂(CO)₁₀ contain ~40 at% Mn for FEBID and a slightly higher metal percentage for CVD. Exclusively insulating material has been observed in FEBID deposits as deduced from electrical conductivity measurements. In addition, strong tendencies for postgrowth oxidation have to be considered.