Real-time in situ atomic force microscopy imaging of bismuth crystal growth

We have performed real-time atomic force microscopy (AFM) imaging of bismuth crystals that were grown under electrochemical control at low overpotentials to ensure a slow growth rate and allow in situ observation of the growth. A two step chronoamperometric potential was applied to a boron-doped diamond (BDD) working electrode with a short high overpotential, -0.4 V (2 s), to nucleate the bismuth, and then a long low overpotential for slow growth, -0.32 V (4.4 h). Growth rates of individual crystals and detailed growth mechanisms could be followed in real time because of the slow crystal growth. The close proximity of the AFM tip and tip holder to the working electrode appears to hinder the diffusion of bismuth to the BDD surface, as evidenced by the significantly lower density of crystals under the cantilever as compared to the rest of the electrode, therefore slowing down the growth process.