Deciphering Spatially‐Resolved Electrochemical Nucleation and Growth Kinetics by Correlative Multimicroscopy

The study employs a multimicroscopy approach, combining Scanning Electrochemical Cell Microscopy (SECCM) and Field Emission Scanning Electron Microscopy (FESEM), to investigate electrochemical nucleation and growth (EN&G). Cu nanoparticles (NPs) are meticulously electrodeposited on glassy carbon (GC), to perform co-located characterization, supported by analytical modeling and statistical analysis. The findings reveal clear correlations between electrochemical descriptors (i-t transients) and physical descriptors (NPs size and distribution), offering valuable insights into nucleation kinetics, influenced by varied overpotentials, surface state, and electrode's area. Analysis of the stochasticity of nucleation reveals intriguing temporal distributions, indicating an increased likelihood of nucleation with higher overpotential and larger electrode's area. Notably, the local surface state significantly influences nucleation site number and activity, leading to spatial differences in nucleation rates unaccounted for in macroscopic experiments. The updated analytical model for EN&G current transients, considering SECCM geometry, shows excellent agreement with FESEM measurements, facilitating the calculation of active sites within individual regions. These results deepen the understanding of EN&G phenomena from a new perspective, and lay the groundwork for further theoretical advancements, showcasing the great potential of current experimental methods in advancing precise electrochemical manufacturing of micro- and nanostructures.