Methods and systems for depositing vanadium nitride layers onto a surface of the substrate and structures and devices formed using the methods are disclosed. An exemplary method includes using a cyclical deposition process, depositing a vanadium nitride layer onto a surface of the substrate. The cyclical deposition process can include providing a vanadium halide precursor to the reaction chamber and separately providing a nitrogen reactant to the reaction chamber. The cyclical deposition process may desirably be a thermal cyclical deposition process.