Atomic force microscopy of the electrochemical nucleation and growth of molecular crystals

In situ atomic force microscopy reveals the morphology, surface topography, and growth and dissolution characteristics of microscopic single crystals of the low-dimensional organic conductor (tetrathiafulvalene)Br_0.76, which are grown by electrocrystallization on a highly oriented pyrolytic graphite electrode in an atomic force microscope liquid cell. The growth modes and the distribution and orientation of topographic features on specific crystal faces, whose identity was determined by "atomic force microscope goniometry," can be correlated with the strength and direction of anisotropic solid-state intermolecular bonding. Growth on the (011) face of (tetrathiafulvalene)Br_0.76 crystals involves the formation of oriented self-similar triangular islands ranging in size from 200 to 5000 angstroms along a side. These nuclei eventually transform into rectangular rafts at larger length scales, where bulk intermolecular bonding interactions and surface energies dominate over nuclei-substrate interactions.