We report on a study of nucleation and growth morphology of diamond microcrystals formed by microwave enhanced chemical vapor deposition. By doping diamonds with boron, sufficient conductivity is achieved that they may be directly imaged by scanning tunneling microscopy with near‐atomic resolution. We demonstrate the first application of work function anddI/dVimaging of diamond. These techniques offer the ability to identify nuclei too small to be recognized by their characteristic cubo‐octahedral shape, and may enable identification of nucleation sites before diamond growth begins.