Carbide coating on nickel to enhance the stability of supported metal nanoclusters.

The influence on the growth of cobalt (Co)-based nanostructures of a surface carbide (Ni 2 C) layer formed at the Ni(100) surface is revealed via complementary scanning tunneling microscopy (STM) measurements and first-principles calculations. On clean Ni(100) below 200 °C in the sub-monolayer regime, Co forms randomly distributed two-dimensional (2D) islands, while on Ni 2 C it grows in the direction perpendicular to the surface as well, thus forming two-atomic-layers high islands. We present a simple yet powerful model that explains the different Co growth modes for the two surfaces. A jagged step decoration, not visible on stepped Ni(100), is present on Ni 2 C. This contrasting behavior on Ni 2 C is explained by the sharp differences in the mobility of Co atoms for the two cases. By increasing the temperature, Co dissolution is activated with almost no remaining Co at 250 °C on Ni(100) and Co islands still visible on the Ni 2 C surface up to 300 °C. The higher thermal stability of Co above the Ni 2 C surface is rationalized by ab initio calculations, which also suggest the existence of a vacancy-assisted mechanism for Co dissolution in Ni(100). The methodology presented in this paper, combining systematically STM measurements with first-principles calculations and computational modelling, opens the way to controlled engineering of bimetallic surfaces with tailored properties.