By using specially constructed nanometer tips of sharpened Pt-Ir wire
in a wax sheath, small numbers of molecules (1-10) can be trapped betw
een the tip and a substrate. Repeated electron transfers of an electro
active molecule as it shuttles by diffusion between tip and substrate
produce a current (similar to 0.6 pA/molecule) that can be used to det
ect the trapped molecules. The tip electrode size and shape can be fou
nd from the electrode approach curves (current vs tip-to-substrate dis
tance) based on approximate equations and digital simulations. Analysi
s of the observed fluctuating currents by autocorrelation, spectral de
nsity, and probability density functions is also described.