212th ECS Meeting, Abstract #1469, The Electrochemical Society

The Influence of Applied Potential on the Impedance of

Alkanethiol SAMs
Harmonie Sahalov,

Brigid OBrien,

Kathleen J. Stebe,

Kalina Hristova, and Peter C. Searson
Department of Materials Science and Engineering, Johns
Hopkins University, Baltimore, Maryland 21218

Self-assembled monolayers (SAMs) of alkanethiols are
routinely used for patterning surfaces, changing surface
wetting properties, or for modifying surface chemistry. In
many of these applications the electrical properties of the
SAM are critical to performance. The electrode potential
is a key parameter in electrodeposition and hence the
potential dependence of the electrical properties of the
SAM are of particular significance.
Self-assembled monolayers are usually considered to
behave as dielectric layers with a capacitance that is
dependent on the monolayer thickness. The
metal/SAM/solution interface is usually modeled as a
series resistance due to the solution, leads, and contacts,
in series with a capacitor associated with the monolayer.
In the absence of electroactive species, the resistance of
the monolayer is infinite and there is no dc current flow
across the interface. Any potential perturbation results in
a transient current due to charging of the monolayer
capacitance. The capacitance of alkanethiol monolayers is
inversely dependent on chain length, consistent with the
parallel plate capacitor model with C =
0
/d, where is
the relative permittivity,
0
is the permittivity of free
space, and d is the distance between the two plates.
More recently, it has been suggested that the simple
ideally polarizable electrode model of self-assembled
monolayers with a solution resistance in series with a
monolayer capacitance is not adequate to describe the
electrical behavior. Impedance spectroscopy
measurements have indicated that there is a conductive
pathway parallel to the monolayer capacitance and that
this parallel resistance is associated with ion permeability
of the SAM.
1, 2

The range of stability of thiol monolayers is bounded at
negative potentials by reductive desorption of the thiol
according to R-S-Au + H
+
+ e
-
R-SH + Au.
3
Since
reductive desorption occurs at negative potentials, there is
a broad potential range of more than 1.5 V where SAMs
are stable. Most prior studies of the electrical properties of
SAMs have been performed near 0 V (Ag/AgCl) and
hence the potential dependence of the electrical properties
of SAMs are, at present, unknown.
In this paper we report on the influence of applied
potential on the impedance of alkanethiols (C
9
H
19
SH,
C
14
H
29
SH, and C
18
H
37
SH) on gold. We show that the
impedance response can be modeled as a parallel network
consisting of the SAM capacitance and resistance over a
large potential range. We also examine the effect of
surface roughness on the impedance of C
18
H
37
SH. While
the SAM capacitance remains constant from positive
potentials to the onset of reductive desorption (see Figure
1a), the SAM resistance exhibits two characteristic
regimes. At potentials positive to -0.3 V (Ag/AgCl) the
resistance is very large and independent of potential,
whereas at more negative potentials, the resistance
decreases exponentially with potential, as shown in Figure
2b. These results show that alkanethiols become
progressively more permeable as the onset of reductive
desorption is approached and highlight the importance of
understanding the influence of the applied potential on the
electrical properties of SAMs.

Figure 1. (a) Capacitance and (b) resistance versus
applied potential for C
18
H
37
SH SAMs on template-
stripped gold (TSG) and evaporated gold.

Figure 2. (a) Capacitance and (b) resistance versus
applied potential for C
9
H
19
SH, C
14
H
29
SH, and C
18
H
37
SH
on evaporated gold.

References
1. Janek, R. P.; Fawcett, W. R.; Ulman, A., Impedance
spectroscopy of self-assembled monolayers on Au(111):
evidence for complex double-layer structure in aqueous
NaClO
4
at the potential of zero charge. Journal of
Physical Chemistry B 1997, 101, (42), 8550-8558.
2. Protsailo, L. V.; Fawcett, W. R., Studies of electron
transfer through self-assembled monolayers using
impedance spectroscopy. Electrochimica Acta 2000, 45,
(21), 3497-3505.
3. Widrig, C. A.; Chung, C.; Porter, M. D., The
electrochemical desorption of n-alkanethiol monolayers
from polycrystalline Au and Ag electrodes. Journal of
Electroanalytical Chemistry 1991, 310, (1-2), 335-359.

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