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Self-assembled monolayers (SAMs) of alkanethiols on gold have become a central focus of controllable surface chemistry because they can be easily formed from the solution phase and characterized using various techniques. Understanding the formation processes occurring at a nanoscale level is crucial to form defect-free SAMs for tailored applications in bio- and nanotechnology. Although many reports study and characterize SAMs after they are formed on gold surfaces, typical methods have not extensively studied the SAM formation process at the nanoscale. This paper focuses on the formation of defect-free SAMs and elucidates the formation mechanism occurring at the nanoscale level during the formation process. Exploiting the strength of scanning electrochemical cell microscopy, we monitored SAM formation via a soluble redox reporter on a polycrystalline gold foil using voltammetric and amperometric techniques. We formed SAMs by varying the concentration of 3-mercapto-1-propanol [HS­(CH2)3OH], 6-mercapto-1-hexanol [HS­(CH2)6OH], and 9-mercapto-1-nonanol [HS­(CH2)9OH] to determine the effects of the thiol chain length, concentration, and location on the substrate (grain boundaries) on monolayer formation. We observed real-time changes in the quasisteady-state current of our redox reporter during the self-assembly process. Importantly, we formed defect-free SAMs at the nanoscale level using different concentrations of HS­(CH2)6OH and HS­(CH2)9OH and found that SAM formation at the nanoscale is concentration-dependent and varies when at a boundary between two crystal grains.

Incorporating the nanoscale properties of carbon nanotubes (CNTs) and their assemblies into macroscopic materials is at the forefront of scientific innovation. The electrical conductivity, chemical inertness, and large aspect ratios of these cylindrical structures make them ideal electrode materials for electrochemical studies. The ability to assemble CNTs into nano-, micro-, and macroscale materials broadens their field of applications. Here, we report the fabrication of random arrays of CNT cross-sections and their performance as nanoelectrode ensembles (NEEs). Single ribbons of drawable CNTs were employed to create the CNT-NEEs that allows easier fabrication of nanoscale electrodes for general electrochemical applications. Surface analysis of the prepared NEEs using scanning electron microscopy showed a random distribution of CNTs within the encapsulating polymer. Electrochemical testing via cyclic voltammetry and scanning electrochemical cell microscopy revealed voltametric differences from the typical macroelectrode response with the steady-state nature of NEEs. Finally, when the NEE was employed for Pb2+ detection using square-wave anodic stripping voltammetry, a limit of detection of 0.57 ppb with a linear range of 10–35 ppb was achieved.