A potentiostatic pulse method has been employed to
electrochemically deposit silver nanocrystallites on the
atomically smooth graphite basal plane surface. Voltage pulses
having amplitudes of 100, 250, and 500 mV
vs Ag0 and durations of 10 or 50 ms were applied to
graphite surfaces immersed in dilute (≈1.0 mM) aqueous
silver nitrate. During the deposition pulse, the current increased
in approximate proportion to (time)1/2 as
expected for an instantaneous nucleation and three-dimensional growth
mode of deposition. Consistent with
this growth mode, noncontact atomic force microscopy (NC-AFM)
examination of graphite surfaces following
silver deposition revealed the existence of silver particles at a
coverage of near 1010 cm-2 which
were well-separated from one another on atomically smooth regions of the graphite
basal plane surface. These particles
were disk-shaped having a height of 15−50 Å and an apparent diameter
which varied from 200 to 600 Å;
particle dimensions increased smoothly with the coulometric loading,
Q
Ag, over the interval from 0.31 to
36
μC cm-2 and in approximate proportion to
Q
Ag
1/3. Significantly, silver
nanocrystallites present on the atomically
smooth regions of a graphite surface could not be observed by using
either the scanning tunneling microscope
(STM) or a conventional repulsive mode atomic force microscope (AFM).
In addition to NC-AFM, the
characterization of these silver nanocrystallites by transmission
electron microscopy lattice imaging and Auger
electron spectroscopy is reported.