Methods of depositing transition metal on a substrate. The disclosure further relates to a transition metal layer, to a structure and to a device comprising a transition metal layer. In the method, transition metal is deposited on a substrate by a cyclical deposition process, and the method comprises providing a substrate in a reaction chamber, providing a transition metal precursor to the reaction chamber in a vapor phase and providing a reactant to the reaction chamber in a vapor phase to form transition metal on the substrate. The transition metal precursor comprises a transition metal from any of groups 4 to 6, and the reactant comprises a group 14 element selected from Si, Ge or Sn.