Focused-Ion-Beam-Milled Carbon Nanoelectrodes for Scanning Electrochemical Microscopy

Nanoscale scanning electrochemical microscopy (SECM) has emerged as a powerful electrochemical method that enables the study of interfacial reactions with unprecedentedly high spatial and kinetic resolution. In this work, we develop carbon nanoprobes with high electrochemical reactivity and well-controlled size and geometry based on chemical vapor deposition of carbon in quartz nanopipets. Carbon-filled nanopipets are milled by focused ion beam (FIB) technology to yield a flat disk tip with a thin quartz sheath as confirmed by transmission electron microscopy. The extremely high electroactivity of FIB-milled carbon nanotips is quantified by enormously high standard electron-transfer rate constants of ≥10 cm/s for Ru(NH₃)₆³⁺. The tip size and geometry are characterized in electrolyte solutions by SECM approach curve measurements not only to determine inner and outer tip radii of down to ~27 and ~38 nm, respectively, but also to ensure the absence of a conductive carbon layer on the outer wall. In addition, FIB-milled carbon nanotips reveal the limited conductivity of ~100 nm-thick gold films under nanoscale mass-transport conditions. Importantly, carbon nanotips must be protected from electrostatic damage to enable reliable and quantitative nanoelectrochemical measurements.