Hindered Surface Diffusion of Bonded Molecular Clusters Mediated by Surface Defects

The design of low dimensional materials through surface assisted self-assembly requires a better understanding of the factors that limit and control surface diffusion. We reveal how substrate surface defects hinder the mobility of submonolayer organic adsorbates on a metal surface with the model CuPc/Cu(111) system. Postdeposition annealing bonds CuPc molecules into dendritelike clusters that are often mobile at room temperature. Surface defects on Cu(111) create energetic barriers that prevent CuPc cluster motion on the metal surface. This phenomenon was unveiled by the motion of small clusters that show rigid-body diffusion solely in the available space in between defects. When clusters are sufficiently surrounded by defects, they become completely pinned in place and become immobilized.