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Electrocarving during Electrodeposition Growth

Shape‐ and size‐controlled synthesis of micro/nanostructures is of fundamental importance in many applications of physics and chemistry. Wet chemical growth methods have achieved shape‐ and size‐controlled synthesis of colloidal nanocrystals of various compositions. Compared with wet chemical methods, electrochemical deposition (ECD) yields micro/nanostructures affixed to a substrate, but the resulting structures are poorly controlled. Herein, the controllable electrochemical fabrication of well‐defined silver‐oxide clathrate micro/nanostructures is realized by intentionally manipulating the previously neglected electrocarving process during electrodeposition growth (MEDEG). Most importantly, the dominance of the electrocarving and the electrodeposition growth process can be immediately manipulated by varying the deposition voltage and/or the composition of the electrolyte. Unique delta‐wing‐, arrowhead‐, and butterfly‐like silver‐oxide clathrate structures are created using the MEDEG method. MEDEG complements the capability of ECD for controllable synthesis of micro/nanostructures of various materials directly on a substrate. The study details the mechanisms that may enable MEDEG to become a competitive alternative to traditional wet chemical methods in the controllable synthesis of micro/nanostructures. This understanding of MEDEG should motivate applications in fields which demand well‐defined micro/nanostructures affixed to a substrate.