This paper reports the results of hot-electron
lifetime measurements in a series of thin films prepared
by
wet chemistry techniques from 12-nm colloidal Au nanoparticles.
The films, which vary in thickness and domain
(or aggregate) size, are studied by a combined approach of femtosecond
optical spectroscopy and scanning probe
microscopy. Atomic force microscope measurements are used to
characterize the samples and quantify the film's
growth pattern. Time-resolved laser spectroscopy measurements are
used to determine hot-electron lifetimes. The
dependence of the hot-electron lifetimes on the colloid film's
structure is analyzed; the lifetimes range from 1 to 3
ps and decrease with greater aggregation. The lifetime is shown to
vary in a predictable manner with the film's
growth, and a model is presented to describe this relationship.
This model allows for the prediction of hot-electron
lifetimes over a broad range of film thicknesses and obtains asymptotic
agreement with previous experimental results
for Au polycrystalline films. Additionally, physical insight into
the processes responsible for the range of lifetimes
is obtained through an analysis that takes into account two competing
phenomena: electron inelastic surface scattering
(ISS), which tends to increase electron−phonon coupling with
decreasing domain size, and electron oscillation−phonon resonance detuning (EOPRD), which tends to decrease it. The
relative contributions of each of these processes
has been estimated and shown to agree with the theoretically-predicted
tends. Finally, these results have implications
for the nature of interparticle coupling and electron mobility.
Specifically, they are consistent with and can be
taken
as evidence for an intercolloid electron conduction mechanism based on
activated hopping. In short, the data presented
herein and their analysis in terms of a size-dependent ISS and EOPRD
shows that in thin films Au colloids aggregate
in such a way as to be electronically coupled with one another while
being physically separated by organic insulating
groups. The films do, however, maintain physical characteristics
and electronic influence based on the colloids
from which they are built.