J. Phys. Chem.

C 2007, 111, 5351-5362 5351

Selective Permeation of a Liquidlike Self-Assembled Monolayer of

11-Amino-1-undecanethiol on Polycrystalline Gold by Highly Charged Electroactive Probes

José M. Campiña,* Ana Martins, and Fernando Silva

Departamento de Quı́mica da Faculdade de Ciências, UniVersidade do Porto,
Rua do Campo Alegre 687, 4169-007 Porto, Portugal
ReceiVed: September 22, 2006; In Final Form: December 13, 2006

Self-assembled monolayers (SAMs) of 11-amino-1-undecanethiol (AUT) have been prepared on polycrystalline

Au by immersion of the corresponding surfaces in an AUT 1 mM solution in pure ethanol. The films were
studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), atomic force microscopy
(AFM), and quartz crystal microbalance (QCM). Results of CV and EIS experiments in NaClO4 solution
agree with the fast formation of a well-packed film with low current density (hundreds of nA/cm2) and
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capacitance values around 2 µF/cm2. The films were stable between -0.7 and 0.7 V (vs Ag/AgCl/NaCl sat.).
Average values of 1.6 nm and 26° were obtained for the film thickness and the tilt chain angle in the potential
region under study. The kinetic analysis of the adsorption process, monitored in situ by the QCM technique,
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showed that it occurs in two stages: a fast Langmuir type adsorption step (k1 ) 0.1047 min-1), followed by
a much slower process of molecular rearrangement (k2 ) 0.0020 min-1). AFM operated in tapping mode did
not reveal any morphological changes on the surface after immersion in AUT discarding multilayer growth.
The electron transfer (ET) of Fe(CN)6-3 and Ru(NH3)6+3 species in solution through the AUT layer was
investigated by CV and EIS. A mechanism of selective permeation of the electroactive species across the
monolayer, controlled by the nature of the electrostatic interactions established at the SAM-solution interface,
explains the experimental data obtained and previously reported in the literature for ET processes through
substituted SAMs. Analysis of the film structure according to theoretical models (commonly used for SAM
characterization) to our experimental data, led to contradictory results clearly affected by the nature of the
unconsidered electrostatic interactions (values of θ ) 0.80 and 0.99 were obtained in the presence of Fe(CN)6-3
and Ru(NH3)6+3, respectively, in KCl electrolyte using the Amatore model).

1. Introduction packed, compact, and defect-free films being these properties

The building of analytical and bioanalytical sensors based
on the deposition of functionalized layers on solid substrates
are gaining widespread importance. Alkanethiol self-assembly
on gold has been used as an efficient method to prepare such
stable and well-defined films that can be modified as for
example by immobilization of macromolecules.1 The preparation
of DNA sensors based on 11-mercaptoundecanoic acid (MUA)3
sets up a well-known example, but the self-assembly processes
of many other thiol derivatives on gold and/or other substrates
have been deeply investigated. Despite the significant effort and
huge number of reported studies on that topic, much of the
aspects related to the structure and the nature of the electron
transfer (ET) processes through these monolayers still remain
unclear.4,5
Chidsey et al.2 studied the alkanethiol, CH3(CH2)nSH, self-
assembled monolayer (SAM) formation on gold and evaluated
their effect on the redox response of highly charged electroactive
species in solution. Almost perfect transfer blocking properties
were obtained for the longer chain thiols (n g 9) while the
electrochemical behavior resembled the corresponding to a
microarray electrode for the shorter ones (n < 7) as the result
of the formation of more disordered templates with a higher
level of defects (pinholes). Consequently, the SAMs of long
chain alkanethiols were described as certainly ordered, close
* Corresponding author. E-mail: jpina@fc.up.pt.
10.1021/jp0662146 CCC: $37.00 © 2007 American Chemical Society
Published on Web 02/28/2007
associated with the compulsory exhibition of a near capacitive,
effective blockage to electroactive species in solution. However,
this description has been contradicted recently for long chain
thiol molecules substituted with terminal-charged electroinactive
but polar groups. The electrostatic interactions established
between these charged groups and the highly charged electro-
active species in solution have shown to govern their own redox
response.6,7,8 In this case, the SAM behaves as an ideal capacitor
or a microarray electrode as a function of the nature of such
interactions. Its influence on the concentration of the electro-
active species in the vicinity of the ET sites has been pointed
out preferably to the hypothesis of pinhole induction and
formation. Considering that most of the popular models used
to estimate defects in SAMs (as the Sabatini and Rubenstein
model,9,10,24 the Amatore model of defects size,25 etc.) are based
on the comparison of the electron transfer on covered and bare
surfaces, it seems that their application for charged SAMs should
originate under- and overestimated results for repulsive and
attractive interactions, respectively. In fact, most of the charged
films studied in the literature were characterized only in
conditions for which repulsive interactions were expected (i.e.,
in the presence of equally charged electroactive solution species
and terminal groups) leading usually to high coverage values
around 99-100%.9,24,43 No additional information about the
results obtained in the presence of opposite-charged species is
usually reported.
5352 J. Phys. Chem. C, Vol. 111, No. 14, 2007
The 11-amino-undecanethiol (AUT) is an 11-fold molecule
with interesting properties for derivatization purposes. The
reactivity of its terminal amine groups gives an opportunity for
further modification and introduction of controlled functionality.
In addition to this, the number of papers about supramolecular
devices based on AUT is much lower in comparison with others
such as MUA. A more thorough characterization of the AUT
films becomes, therefore, a fundamental task before proceeding
to the modification and building of AUT based devices and,
additionally, an opportunity to improve our knowledge about
the ET phenomena through these films. In this paper the
preparation, structure and performance of AUT monolayers were
studied by cyclic voltammetry (CV), electrochemical impedance
spectroscopy (EIS) and atomic force microscopy (AFM). The
kinetics of the adsorption process was also studied by means
of the quartz crystal microbalance (QCM) technique. The nature
of the ET processes of Fe(CN)6-3 and Ru(NH3)6+3 solution
species through the AUT layer was additionally investigated
by electrochemical means.
2. Experimental Section
2.1. Chemicals and Solutions. 11-Amino-1-undecanethiol
hydrochloride (AUT, Dojindo Laboratories), K3Fe(CN)6 (Merck,
p.a.), Ru(NH3)6Cl3 (Aldrich, 98%), NaClO4‚H2O (Merck p.a.),
NaF (Merck, suprapur), KCl (Merck, p.a.), ethanol (Aga, 96%
vol.), N2 (N45, Air Liquid) and all other chemicals were
analytical grade and were used as received. Five different
solutions were prepared for the electrochemical characterization
of the SAM. Solution E refers to a NaClO4 0.3 M electrolyte
solution. For the experiments in the presence of electroactive
species, the following solutions were prepared: NaF 0.2 M +
K3Fe(CN)6 2 mM (A); NaF 0.2 M + Ru(NH3)6Cl3 2 mM (B);
KCl 0.2 M + K3Fe(CN)6 2 mM (C); and KCl 0.2 M + Ru-
(NH3)6 Cl3 2 mM (D). The pH was not adjusted to avoid the
unexpected effect of the buffer reagents. The values obtained
for solutions A-D, using a Methrom 654 pH meter, were 7.82,
7.86, 5.46, and 5.04, respectively. The pKa of a self-assembled
monolayer of AUT on Au has been estimated as ≈7.5 from the
results reported by Degefa et al. (Figure 1.I in ref 7). It is shown
there that the peak current for the redox process of Fe(CN6)-3/-4
species through an AUT monolayer suffers a great decrease in
the pH region between 7 and 8 and that it is not effectively
blocked until the pH is higher than 8. CVs obtained for a SAM
of cystamine on Au in the presence of the same electroactive
probe showed just a partially blocked profile even at a pH of
8.1.8 Consequently we should have at least partially charged
monolayers in all cases. A solution of 8 mL of AUT 2 mM in
ethanol was prepared for the QCM experiments. All the aqueous
solutions were prepared in ultrapure water from a Milli-RO 3
Plus, coupled with a Milli-Q water purification system with a
resistivity value of 18 MΩ cm.
2.2. SAM Preparation. AUT films were prepared on a gold
polycrystalline rod electrode to apply electrochemical methods
as follows. First, the electrode was decontaminated according
to the Clavilier method.15 After treatment in a butane-air flame,
the electrode was rinsed with ultrapure water then with ethanol
and quickly immersed in an AUT 1 mM solution in ethanol. It
was kept there for the investigated time. Finally, it was removed
and copiously rinsed in ethanol and ultrapure water. This
procedure was conducted prior to every electrochemical experi-
ment. Preparation of AUT monolayers on Au polycrystalline
slides was performed following a similar procedure. The Au
slides were rinsed three times alternately in pure ethanol,
acetone, and ultrapure water, dried in a N2 flow, and immersed
Campiña et al.
in the AUT solution. After removal, the slides were rinsed in
ethanol. A final drying step in N2 was applied previous to the
AFM characterization.
2.3. Cyclic Voltammetry. Experiments were performed in
a three-electrode cell under N2 flow using a Voltalab PGZ301
potentiostat (from Radiometer Analytical) controlled by Vol-
taMaster 4 software. A Ag/AgCl/NaCl saturated electrode (in
a separated compartment containing the electrolyte and con-
nected by a salt bridge to the main cell) and a helix-shaped
gold wire were used as reference electrode and counter electrode,
respectively. A bulk gold polycrystalline electrode with a surface
area of 0.11 ( 0.05 cm2, estimated by the method of the
electrochemical reduction of an AuO monolayer,11-14 was used
as the working electrode in all cases. The contact between the
electrode surface and the solution was made by means of the
hanging meniscus method.31 Unless otherwise indicated, CV
was performed at 50 mV/s scan rate.
2.4. Electrochemical Impedance Spectroscopy. Impedance
spectra were registered at 10 mV amplitude, 10 kHz to 500
mHz frequency range, using the same Voltalab PGZ301
potentiostat. Through the use of the Eco Chemie frequency
response analyzer (FRA) 4.9 software, the data obtained were
fitted to: (a) a RQ equivalent circuit (i.e., a resistor R (electrolyte
resistance) in series with a constant phase element (CPE) Q,
for experiments in supporting electrolyte) and (b) a Randles
circuit in the presence of electroactive species.42 The CPE is a
power-law dependent interfacial capacity accounting for the
topological imperfections, originated by the different crystal
facets, and the surface roughness. FRA considers the admittance
of a CPE as
Y ) (Qoiω)n (1)
The fitted values of n and Qo are supplied by the software.
However, the admittance of a CPE is more commonly described
as
YCPE ) Yo(iω)n (2)
Comparing eqs 1 and 2, we must conclude that the fitted
values of Qo must be raised to the n power to obtain Yo in their
main units of secn Ω-1. When n ) 1, the CPE is equivalent to
an ideal capacitor18 and Yo ) Cdl, where Cdl is the corresponding
double-layer capacitance in F. For experiments in pure elec-
trolyte, n g 0.97 was obtained in all cases suggesting that the
surface of the AUT-modified electrode is only slightly rough
and behaves almost as an ideal capacitor. This assumption is
not free of small error, but allows considering the area corrected
values of Yo as electrode capacitances. However, G. J. Brug et
al.49 indicated that the double-layer capacitance of an ideal
polarized electrode is more appropriately represented by
Cdl ) (Yo)1/n (RΩ)1-n/n (3)
This is equivalent to writing
Cdl ) Qo(RΩ)1-n/n (4)
In these expressions, RΩ represents the solution resistance.
Additionally, Hsu and Mansfeld52 suggested the following
correction for the case of a depressed semicircle (as observed
in the presence of electroactive species):
Cdl) Yo(ωmax)n-1 (5)
Selective Permeation of AUT Monolayers on Au
Figure 1. The first (s), second (- -), third (- ‚), and fourth (- ‚ ‚)
consecutive CVs, obtained for a 24 h AUT modified Au electrode, are
compared with the CV for the bare Au (...) in NaClO4 0.3 M. The scan
rate was 50 mV s-1 in all cases.
with ωmax corresponding to the frequency at which the imaginary
component of the impedance reaches a maximum in the
semicircle region of the Nyquist plot. The capacitance values
obtained using eqs 4, 5 were divided by the working electrode
area (A). The final capacitance values presented in this work,
consist on the average of five independent measurements (with
their corresponding standard deviation) performed at each
potential. This point becomes very important because details
on the capacitance calculation are not generally discussed in
the literature.
2.5. Atomic Force Microscopy. AFM imaging was per-
formed in air using a PicoLe atomic force microscope (Molec-
ular Imaging, USA) operated in tapping mode using n+-silicon
cantilever/tips (Nanosensors, cantilever force constant of 25-
50 N/m). Commercial 1.8 × 1.8 cm gold polycrystalline slides
(EMI) were used as substrates. The images were scanned in
topography, amplitude, and phase mode with a resolution of
512 × 512 pixels and were representative of at least five 1 ×
1 micrometer images taken over different locations on the
studied surfaces.
2.6. Quartz Crystal Microbalance. The AUT adsorption
process was studied in situ using a Picobalance V3 oscillator,
from Technobiochip Scarl, controlled by Picoview 3.0 software.
10 MHz overtone polished AT-cut plano-plano quartz crystals
coated with gold electrodes (5 mm diameter) on both sides and
connected to the oscillator by chromium spring contacts were
purchased from International Crystal Manufacturing (ICM) Co,
Inc. The experiments were performed exposing just one side
of the quartz plate to the solution phase. Pure ethanol was
injected into the cell after probe equilibration in ambient air. It
was followed by the addition of the concentrated thiol solution.
The resonance frequency shift of the quartz crystal was then
recorded in a time-resolved manner.
3. Results and Discussion
3.1. Electrochemical Characterization in Electrolyte Solu-
tion. Four consecutive CVs obtained (increasing progressively
the potential limits from (0.5 V to (1.250 V) for a 24 h AUT
immersed Au electrode in solution E are compared with the
CV obtained for the bare Au electrode in Figure 1. A
significantly lower current density (>10 times at 0.5 V) was
observed for the first recorded cycle when compared to the bare
J. Phys. Chem. C, Vol. 111, No. 14, 2007 5353
Figure 2. CVs registered in NaClO4 0.3 M for an Au electrode
previously immersed in AUT 1 mM solution for 30 min (s), 1 h. (-
-), 2 h. (- ‚), 6 h. (- ‚ ‚), 12 h. (‚ - ‚ -), and 24 h. (...) in NaClO4 0.3
M. Scan rate: 50 mV s-1.
Au. The blocking properties of the modified electrode showed
to be stable within a potential region of ( 0.7 V. As the potential
window was extended beyond these values, an oxidation current
was observed consistent with the electrochemical desorption of
SAMs.16 The process showed to be irreversible reverting to a
voltammetric profile that resembled the one for the bare Au
just after four cycles.
The effect of the immersion time was also investigated from
30 min to 24 h. The modified electrodes were studied by CV
within the previously determined region of potential stability
and their comparison is shown in Figure 2. No significant
differences in shape and current density (which fell in the order
of few hundreds of nA/cm2 in all cases) were observed. EIS
experiments showed good agreement with the voltammetric data.
The Nyquist plots recorded at 0.150 V for the modified
electrodes and the bare Au in NaClO4 0.3M are shown in Figure
3A. No significant differences were observed between the
different AUT immersed electrodes, which exhibited a linear
response close to the typical behavior of a pure capacitor. The
Bode and Bode phase plots obtained for two different immersion
times (30 min and 24 h) and for the bare Au electrode are shown
in Figure 3B. The values of log |Z| obtained for the latter were
lower than those obtained for the AUT immersed electrodes in
the whole frequency domain, which confirms that these modified
electrodes exhibit stronger capacitor behavior. Theoretically, the
SAM behavior is well described by the Helmholtz ideal
capacitor model when the phase angle at 1 Hz is 90°.18 At higher
frequencies, the total impedance is controlled by the solution
resistance. Phase angles higher than 88° in the medium-low-
frequency region (1-1000 Hz) are considered in practical terms
to correspond to pure capacitor behavior. Bode phase plots for
the modified electrodes exhibited a value close to 90° in a wider
range of frequencies than for the bare Au confirming their
enhanced capacitor character again. No significant difference
was observed in the Bode and Bode Phase plots for both
immersion times. The impedance data were fitted to an RQ
equivalent circuit. The capacitances obtained at 0.150V, as
described in the experimental section, for the different immer-
sion times and for the bare Au are presented in Table 1. After
immersion in the thiol solution, the capacitance strongly
decreased from values of 20 µF/cm2 (obtained for Au) to
approximately 2 µF/cm2 found for the modified electrodes.
These values are in good agreement with the reported for
alkanethiol SAMs with more than 10 methylene groups (1-5
µF/cm2 1,21) and with the ones for Au electrodes (between 20
and 50 µF/cm2 depending on the applied potential and the
electrolyte composition1,45). Capacitances obtained at three
different potentials for the films prepared with 24 h and 30 min
5354 J. Phys. Chem. C, Vol. 111, No. 14, 2007 Campiña et al.

Figure 3. (A) Nyquist plots registered at 0.150 V for the different AUT immersed electrodes: 30 min (0), 1h (O), 2h (4), 6h (3), 12h ("), 24h
(<), and the bare Au electrode (b) in NaClO4 0.3 M. (B) Corresponding Bode plots and Bode phase plots for different immersion times: 30 min
(0, - -), 24 h. (<, ...) and the bare Au electrode (b, s).

TABLE 1: Capacitances Obtained by Fitting the Impedance TABLE 3: Film Thickness (d) and Tilt Chain Angle (r)
Data in Figure 3 to an RQ Circuit Obtained from Data in Table 2a
electrode C (µF/cm2) E (V) d24h (nm) R24h (deg)
Au/AUT 30 min 2.0 ( 0.1 -0.20 1.7 19
Au/AUT 1h 2.4 ( 0.1 0.15 1.6 27
Au/AUT 2h 2.1 ( 0.1 0.20 1.6 32
Au/AUT 6h 2.0 ( 0.1 Average 1.6 26
Au/AUT 12h 2.2 ( 0.1 a
Au/AUT 24h 2.1 ( 0.1 Data obtained for an electrode prepared with a self-assembly time
Au bare 20 ( 7 of 24 h.

TABLE 2: Capacitances Obtained from EIS Measurements
in NaClO4 0.3 M at Different Potentials after 30 min and 24
h Immersion Times
E (V) C24h (µF/cm2) C30m (µF/cm2)
-0.20 2.0 ( 0.1 1.9 ( 0.1
0.15 2.1 ( 0.1 2.0 ( 0.1
0.20 2.2 ( 0.1 1.9 ( 0.1
average 2.1 ( 0.1 1.9 ( 0.1
of self-assembly are included in Table 2. The average values
in the potential range explored were very close, showing no
significant difference (2.1 µF/cm2 for the 24 h and 1.9 µF/cm2
for the 30 min immersion). These results are consistent with
the formation of a relatively well-packed monolayer on the
surface with electrical insulating properties at even shorter times
than those investigated. This agrees well with the previous
reported data for alkanethiol adsorption on Au in which the
process is described to occur in a time ranging from milliseconds
to minutes and to be followed by slow self-organization
processes (taking place in hours or days) leading to more ordered
structures.3,17,16 The detail in Figure 3A shows the very slight
increase of the slope registered in the Nyquist plots with the
immersion time in AUT (the lowest slope was observed for the
bare Au electrode), which could be related with these rearrang-
ing processes. Therefore, we can say that the self-assembly
occurs in its greater extent for immersion times shorter than 30
min.
The capacitance data were used for the estimation of the film
thickness. As it has been shown previously,2,20-24 the behavior
of these alkanethiol assemblies resembles that predicted by the
Helmholtz model of electrical double layer. According to this
model, the double layer is described as an ideal parallel plate
condenser
C ) A0/d (6)
A corresponds to the plate surface area, 0 is the free space
permittivity constant (8.84 × 10-12 F/m), d is the plate distance,
and  is the dielectric constant for the medium. Different values
of  have been reported in the literature for substituted and
nonsubstituted self-assembled alkanethiols on mercury and gold
surfaces ranging from 2 to 4.2,3,21-23,43,51,53 Under the reasonable
assumption that the dielectric constant for AUT films is not
very different from MUA films, a value of  ) 3.953 was used
in eq 6 to estimate the thickness (d) of the AUT film.
Calculations were made using the capacitance values obtained
for a 24 h immersed electrode. Table 3 summarizes the data
obtained that indicate that the film thickness slightly decreases
as the potential increases from -0.2 to 0.2 V. An average value
of 1.6 nm was obtained, which is close to the previously
estimated value of 1.8 nm for MUA.53
By simple trigonometry it is also possible to estimate the tilt
angle (R) of the AUT organic chains with respect to the surface
normal as
cos R ) d/L (7)
The molecular length of the AUT molecule (L) was estimated
by means of computational molecular mechanics calculations
MM2 (Chem3D Ultra 8.0 software, CambridgeSoft Corpora-
tion). The energy minimization of an AUT single molecule
adopting a fully extended chain conformation led to a value
for the distance between the sulfur atom and the furthest
hydrogen (in the amino terminal group) of 1.6352 nm, which
is comparable with the 1.61 nm reported for the MUA molecule
by F. Cecchet et al.43 A final value of L ) 1.8352 nm was
obtained by the addition of 0.2 nm to account for the Au-
sulfur distance.53-55 The angles obtained in the potential range
studied are also shown in Table 3 (from 19 to 32°) and showed
higher dispersion than the values of the film thickness.
Considering the assumptions underlying the estimation of these
parameters by electrochemical techniques (especially in the case
of tilt angles), no particular attention must be paid to the changes
observed by sweeping the applied potential although the possible
establishment of potential-induced structural changes (as phase
transitions, etc.) in the film should be further investigated by
Selective Permeation of AUT Monolayers on Au
Figure 4. Time-resolved resonance frequency shift of a 10 MHz quartz crystal plate immersed in 8 mL of pure ethanol upon the addition of 2
consecutive aliquots, labeled as A and B, of 4 mL AUT 2 mM in ethanol (s). The final AUT concentration in the Teflon chamber was 1 mM. Data
fittings to a simple (blue line) and double (red line) exponential equations are included.
other techniques. Thus, the average value of 26° should be taken
as the most characteristic angle obtained for the film, which is
close to the 28° measured using ellipsometry and IR spectros-
copy by Allara et al.2,50 for SAMs of n-alkanethiols on Au
surfaces. Other reported values around 20 and 40° have been
found in literature3,20,43 for the films formed by different kinds
of alkanethiols on Au.
3.2. Adsorption Rate. The self-assembly process of AUT
on Au was followed in situ by time-resolved QCM measure-
ments. The change in the resonance frequency (∆f) suffered by
a quartz plate in air is associated with both changes in the crystal
and in the deposited mass (∆m) on it, according to Sauerbry et
al.32 As it has been proven in different works with polyelec-
trolyte adsorption,39,40 the frequency changes in aqueous media
are usually larger than the observed in ambient air due to several
frictional factors or overadsorption. Considering that the adsorp-
tion rate is both proportional to the thiol solution concentration
(which is constant) and the number of uncovered sites on surface
(simple Langmuir adsorption), Kunitake et al.41 derived the
following kinetic equation:
Ln[(F - F∞)/(F0 - F∞)] ) -kt (8)
where F is the resonance frequency at a given time t, F0 is the
initial frequency, and F∞ is the frequency at the end of the
adsorption process. Considering the frequency shift after a time
t as ∆F ) F - F0, the final frequency shift as ∆Ff ) F∞ - F0
along with integrating eq 8 is the following:
∆F ) ∆Ff (1 - e-kt) (9)
In a typical in situ QCM measurement, the resonance
frequency decreases exponentially with time. The additions of
2 aliquots of 4 mL of AUT 2 mM (labeled as A and B in Figure
4) were done in 2 consecutive steps, separated by less than 1
min, to minimize the effect of the vibrations caused by the
addition of such a large volume in the plot but it could not be
totally avoided. Monitoring of the resonance frequency started
minutes before any addition. The decrease in the resonance
frequency of the crystal corresponding to the thiol adsorption
was followed for approximately 2 h when the maximum
J. Phys. Chem. C, Vol. 111, No. 14, 2007 5355
frequency shift was reached. Fitting the experimental data to
eq 9 gave a very poor result (see blue line in Figure 4). As it
has been addressed previously, the adsorption of n-alkanethiols
on Au has been described to occur in two different steps:3,16 a
first and fast Langmuir type adsorption,33 which is usually
followed by much slower film reorganization processes at high
coverage.3,16,34-37 Additionally, the transition from the low
coverage striped phases to the standing up configurations has
been pointed as the significant kinetic bottleneck of such
mechanism.16 The use of a double exponential kinetic law has
proved to be useful to obtain the kinetics of other similar
complex adsorption processes, as follows40
∆F ) ∆F1 (1 - e-k1t) + ∆F2 (1 - e-k2t) (10)
where ∆F1 and ∆F2 are the maximum frequency shifts for each
adsorption step and k1 and k2 their corresponding rate constants.
The experimental data were best fitted to this kinetic law (R2
) 0.98819; red line in Figure 4), which seems to confirm (in
addition to the evidence found in the small increase of the slope
in the Nyquist plots; detail in Figure 3A) the establishment of
slow self-organization processes leading to the formation of
slightly highly ordered and close-packed structures with the
increase of the immersion time. A rate constant of k1 ) 0.1047
min-1 was obtained for the first adsorption process while a much
lower one, k2 ) 0.0020 min-1, was obtained for the second
step.
The thiol coverage after a given adsorption time t, can be
estimated from QCM data using the following expression:
θQCM ) ∆F(t) /∆Ff (11)
where ∆F(t) is the frequency shift for an adsorption time t and
∆Ff is referred to the saturation shift The frequency shift
obtained 30 min after the second addition (t ≈ 33 min) had a
value of -22 Hz, which corresponds to a coverage value of
0.666. This result agrees with the observed electrochemical
behavior in NaClO4 0.3 M suggesting the formation of a
monolayer with a reasonable coverage just after 30 min
immersion that is slowly increased with the immersion time in
AUT.
5356 J. Phys. Chem. C, Vol. 111, No. 14, 2007
Figure 5. Cyclic voltammograms for the bare (s) and a 24 h AUT immersed (...) Au electrodes in: (A) NaF 0.2 M + K3Fe(CN)6 2 mM, (B) NaF
0.2 M + Ru(NH3)6Cl3 2 mM, (C) KCl 0.2 M + K3Fe(CN)6 2 mM, and (D) KCl 0.2 M + Ru(NH3)6Cl3 2 mM. Scan rate: 50 mV s-1.
3.3. Electrochemical Characterization in the Presence of
Electroactive Species. The AUT film was studied by CV and
EIS in the presence of the highly charged electroactive ions
Fe(CN)6-3 and Ru(NH3)6+3 (2 mM) in two different electrolytes,
NaF and KCl 0.2 M (solutions A-D). With the purpose of
building the best possible organized and compact monolayer
on the surface, the AUT film was prepared with a self-assembly
time of 24 h in all cases. The voltammograms obtained for the
bare and the modified electrode are presented in Figure 5.
Almost diffusion-controlled profiles were obtained for the
modified electrode in solutions A and C (Figure 5A,C).
However, the redox response was strongly blocked in solutions
B and D (Figures 5B and 5D). These results agree well with
the previous observations made by other authors in KCl
electrolyte6,7 and, moreover, confirm the reproducibility of this
behavior even in a different electrolyte such as NaF. The
establishment of electrostatic interactions between the charged
terminal groups in the SAM (NH3+ groups in AUT) and the
negative Fe(CN)6-3/-4 anions (attractive interactions) and the
positive Ru(NH3)6+3/+2 cations (repulsive) in solution was
suggested in these works as the reason for the observed
electrochemical response. They reported that the effect of such
interactions on the concentration profiles of the redox probes
in the surroundings of the ET active sites determined the
observed redox behavior giving no very convincing explanations
about the electron-transfer mechanism.
EIS was performed in the same conditions to obtain additional
insight into the transfer mechanism. The Nyquist plots registered
for the bare and the AUT modified Au electrode in solutions
A-D at their corresponding half-wave potentials (0.200 V for
the [Fe(CN)6]-3/-4 and -0.150 V for the [Ru(NH3)6]+3/+2 redox
couples) are presented in Figure 6. The results were analyzed
and fitted in terms of a Randles equivalent circuit.42 A typical
Nyquist plot for this circuit presents a semicircle in the high-
medium-frequency region at which the total impedance is
Campiña et al.
controlled by the charge-transfer resistance RCT and a linear
region at low frequencies in which the semi-infinite linear
diffusion governs the process. The small semicircle registered
for the bare Au electrode (full circles in Figure 6) in the presence
of both ions is associated to a fast electrode reaction. However,
a wider and better defined, semicircle was obtained for the AUT
modified electrode in the four studied solutions. This feature is
associated to a higher value of RCT, showing that the insulating
properties of the SAM hinder the ET processes of such probes.
Nevertheless, this effect was much stronger in the presence of
hexaamineruthenium than for the hexacyanoferrate as indicated
by the 10 times wider semicircle. The Nyquist plots obtained
in the presence of the ruthenium species also showed the absence
of a linear region at low frequencies suggesting that the process
is not controlled by mass transport in that case.
The capacitance and the RCT values were derived from the
fitting of the impedance data to the Randles circuit (Tables 4
and 5). The capacitance values obtained for the modified
electrode in Ru(NH3)6+3 solutions were close to 2 µF/cm2 in
the same order of those obtained in NaClO4 0.3 M pure
electrolyte. On the other hand, they were close to those obtained
for the bare Au electrode in perchlorate electrolyte when the
solution contained Fe(CN)6-3 (especially in KCl). Both, the
voltammetric and capacitance results suggest that the electro-
static interactions at the SAM-solution interface are determinant
in the overall process. While the repulsive interactions suffered
by the Ru(NH3)6+3/+2 cations seem to keep its concentration
low near the ET active sites (with small consumption of species
and, consequently, high charge-transfer resistances and negli-
gible contribution of the mass transport to the Nyquist plots),
the attractive interactions felt by the Fe(CN)6-3/-4 anions favor
their transport to such sites, which is confirmed by the lower
RCT, the marked contribution of the mass transport to the
impedance spectra, and the well-developed and intense current
peaks obtained in the voltammetric profiles.
Selective Permeation of AUT Monolayers on Au
Figure 6. Nyquist plots obtained for the bare (b) and a 24 h AUT immersed (O) Au electrodes in: (A) NaF 0.2 M + K3Fe(CN)6 2 mM, (B) NaF
0.2 M + Ru(NH3)6Cl3 2 mM, (C) KCl 0.2 M + K3Fe(CN)6 2 mM, and (D) KCl 0.2 M + Ru(NH3)6Cl3 2 mM at their equilibrium potentials. The
amplitude of the perturbation was of 10 mV in all cases.
TABLE 4: Capacitances Obtained by Fitting the Impedance
Data in Figure 6 Compared with Those Obtained in NaClO4
0.3 Ma
electrode C (µF/cm2)
bare Au in E 20 ( 7
Au/AUT in E 2.1 ( 0.2
Au/AUT in A 7(2
Au/AUT in B 2.3 ( 0.1
Au/AUT in C 24 ( 5
Au/AUT in D 2.2 ( 0.1
a The capacitance values correspond to a 24 h immersed Au electrode
in solutions A and C (at 200 mV), B and D (at -150 mV), and for the
bare Au in solution E (at 150 mV).
It is possible to find in the literature several references
reporting evidence about the distortion of the dense and compact
archetypal (x3 × x3) R30° structure found for long chain
alkanethiols on Au(111) by the inclusion of terminal bulky or
charged groups. The works of J. M. Stirling et al.20 and an
excellent review by F. Schreiber46 claimed that this archetypal
order could be reached unless it was sterically prohibited and/
or disrupted by endgroup-endgroup interactions. These conclu-
sions were based on the evidence found, among others, by
Himmel et al.47-48 using NEXAFS and XPS to study the films
formed by HS(CH2)16OH and HS(CH2)16COOH. Tilt angles
between 39 and 44° were found in contrast with the 28° found
by Chidsey2 for unsubstituted thiols, which was in conflict with
the maximum packing given by the Van der Waals radii if a
(x3 × x3) R30° is assumed. On the other hand, the nature of
these SAMs is responsible of complex phase transitions
(especially at the solid-liquid interface). The organic chains
are canted and the chain-chain interactions (van der Waals,
dipole-dipole) are less energetic than the S-Au bond, which
converts the structure sensitive to the temperature. That is on
J. Phys. Chem. C, Vol. 111, No. 14, 2007 5357
the origin of a variety of thermally driven gauche conformers
and tilt-order phase transitions even at room temperature. This
dynamic behavior allows that these films could be described as
liquid-like structures.1,16 The final structure of the AUT films
should arise from the balance of three types of interactions: the
S-Au bonding, the chain-chain interactions, and the -NH3+
self-repulsion. With the inclusion of the latter repulsive interac-
tion, the formation of a relatively more disordered film should
be expected when compared to undecanethiol. The impact on
its structure will depend on the strength of this interaction, as
Schreiber remarked, but at least a higher disorder in the
outermost part of the film should be expected. In addition to
this, the breaking of CH2-CH2 units should be facilitated in
this part of the film as the effect of the endgroup-endgroup
repulsion. This fact, combined with its dynamical behavior,
could explain the redox response registered by CV and EIS
without the need of the existence of a significant amount of
extrinsic pinholes (those related to the characteristics of the
substrate and the purity of the adsorbate solutions: pitlike
defects, defects at grain boundaries, etc. in the structure.
Accordingly, a membrane model that takes in consideration the
disorder induced by the amino-amino self-repulsion, the
dynamical behavior of the chains, and the minimum contribution
of the extrinsic pinholes to the permeation of the structure (as
suggested by the results in pure electrolyte) is considered. Such
a membrane may present selective permeability controlled by
the established electrostatic interactions at the SAM-solution
interface. The selective membrane will facilitate or hinder the
transport of charged probes according to the nature of the
interactions: attractive interactions (as observed for the hexacy-
anoferrate) and repulsive interactions (as in the presence of
hexaamineruthenium cations). Results in the literature6-8 could
also be explained by this model. For instance, the pH depen-
5358 J. Phys. Chem. C, Vol. 111, No. 14, 2007
TABLE 5: Charge-Transfer Resistance (RCT)a and Other Structural Parametersb
RCT σW
electrode (Ω) θR (Ω cm2 s-1/2)
Au/AUT in A 906 0.865
Au/AUT in B 80600 0.999
Au/AUT in C 769 0.496
Au/AUT in D 25080 0.999
Bare Au in A 122 192
Bare Au in B 54 100
Bare Au in C 387 127
Bare Au in D 20 126
aR b
CT was obtained by fitting the impedance results in Figure 6. The structural parameters θR, θDS, ra, and rb were calculated applying the
Sabatini and Rubenstein and the defects size model to the results obtained by fitting the impedance data obtained from Figure 6.
Figure 7. Voltammetric profiles consecutively obtained for a 24 h
AUT immersed Au electrode in: (A) KCl 0.2 M + K3Fe(CN)6 2 mM,
details show the slow decrease in the peak current; (B) KCl 0.2 M +
Ru(NH3)6Cl3 2 mM, details show the progressive growth of the peaks
with time. The first cycle recorded after the electrode-solution contact
is a dot line in both cases. Scan rate: 50 mV s-1.
dence of the voltammetric response of such probes found by
Degefa et al.7 (Figure 1.I in ref 7) could be rationalized in terms
of the effect of the protonation-deprotonation processes on the
charge of the terminal amine groups and, thus, in the nature of
the electrostatic interactions and the permeation of the layer.
Another important observation can be made from the previ-
ously presented voltammetric experiments in the presence of
[Ru(NH3)6]+3/+2. It was observed that the initial-blocking
behavior obtained for the transfer process partially disappeared
sometime after the beginning of the experiment. Further CV
experiments were performed in solutions C and D in a dynamic
way (i.e., registering the evolution of the redox response since
the first contact SAM-solution over periods longer than 4 h).
Some selected voltammetric profiles obtained in both solutions
are shown in Figure 7. While a slight decrease in the redox
activity was registered in solution C (from cycle 1 to cycle 4 in
Figure 7A), a spectacular transition was obtained in the case of
hexaamineruthenium from blocking behavior (cycle 1 in Figure
7B) to microelectrode behavior (cycle 13). Details in the figure
show that the current increased progressively with time (cycles
1-5 and 6-12) and the large extension of the total transition
(comparison between cycles 1 and 13). Figure 7B reports
evidence of the establishment of a time dependent process
affecting the nature of the electrostatic interactions and,
consequently, the ET properties. EIS experiments were also
taken in the same solutions at discrete time intervals much
shorter than the time necessary to observe significant alterations
in the film. Any change during the collection of one individual
plot should have little effect on the spectrum and mainly in the
low-frequency region. Figure 8 shows some selected Nyquist
plots taken at contact times larger than 4 h. In the presence of
hexacyanoferrate (Figure 8A), the shape of the plots showed a
transition to longer semicircle diameters reaching, finally, a
Campiña et al.
m ra rb
(Ω cm2 s-1/2) θDS (µm) (µm)
1210 0.84 1.7 4.4
21571 0.995 9.6 140.3
633 0.799 3.3 7.5
13316 0.990 5.3 54.9
steady profile (plot 20). Nevertheless, the reverse situation was
found in the case of hexaamineruthenium with the diameter
decreasing with time. In the last case, the plots did not show
any linear contribution at low frequencies for the shorter contact
times. However, as it is shown in the details of Figure 8B, such
linear contribution started to develop for longer contact times
(plots 10-11).
Several explanations can be proposed for this behavior. The
simplest one is related to the possible desorption of the SAM
after immersion in KCl. In the progressive desorption of the
monolayer with the contact time, the magnitude of the electro-
static interactions should also decrease. A decrease in the
repulsive interactions toward the hexaamineruthenium cations
would favor its transport to the active sites and, thus, the whole
ET process. On the other hand, the decrease in the intensity of
the attractive interactions established by the terminal amino
groups toward the hexacyanoferrate species should affect its
transport to such sites as well. But at the same time, the coverage
reduction could favor the process. As a net effect, the process
could become slightly hindered. To check this hypothesis,
voltammetric and impedance data for an AUT-covered electrode
were recorded after immersion in KCl 0.2 M over 1 day. Figure
9A shows the voltammetric profiles obtained for the modified
electrode in this electrolyte after the first contact electrode-
solution (dash line) and after more than 1 day immersed in it
(dot line). For comparison, the profile for the bare Au in the
same media is also shown (straight line). The data bring no
support to the hypothesis of desorption of the SAM. The same
conclusion is reached by comparing the Nyquist plots in Figure
9B. The detail placed at the bottom shows that the slope of the
line and, thus, the capacitance are barely affected indicating
that the structure and the composition of the film did not vary
significantly. The same conclusion is reached analyzing the Bode
and Bode phase plots in the other detail of the figure.
As the highly charged electroactive ions can feel the attractive
(or repulsive) interactions from the SAM terminal groups, so
should the electrolyte ions (although less intensely because of
their lower charge). While electrolyte cations should feel
repulsive interactions and on average keep far from the
positively charged surface of the AUT film, it should be
interesting to consider the behavior of the anions. Degefa et
al.7 reported the competition between the electroactive and
nonelectroactive ions for the available surface sites on an
oppositely charged SAM. An alternative explanation for the
transitions observed while increasing the contact time could be
related to the neutralization of the charged terminal groups by
electrostatic binding of the electrolyte anions, which were in a
much higher concentration than the electroactive ones. The
progressive neutralization of the surface would affect, conse-
quently, the nature of the electrostatic interactions established
with the electroactive species at the interface and the electron-
Selective Permeation of AUT Monolayers on Au J. Phys. Chem. C, Vol. 111, No. 14, 2007 5359

Figure 8. Nyquist plots for a 24 h AUT immersed Au electrode in: (A) KCl 0.2 M + K3Fe(CN)6 2 mM. Details show the growing of the
semicircle region. Full and open symbols are used for better visualization. (B) KCl 0.2 M + Ru(NH3)6Cl3 2 mM. Details show the development of
linear region. The gap observed between curves 9 and 10 is due to the breaking of the hanging meniscus.

Figure 9. CV and EIS experiments in KCl 0.2 M for an 24 h. immersed electrode after the first contact with solution (dash lines, open circles),
after 24 h immersed in such solution (dot line, open triangles) and the bare Au (straight line, full circles). (A) CV for these electrodes. Scan rate:
50 mV s-1. (B) Nyquist plots obtained in the same conditions. The details show the Bode plots and the Bode phase plots for the same electrodes.
Amplitude: 10 mV.

transfer properties through the film. The reduction of the overall
surface charge will favor the permeation of the hexaamineru-
thenium species while it will just slightly hinder the processes
of hexacyanoferrate species. Figure 10 shows an art model
describing this process in the presence of hexaamineruthenium
species.
The structural parameters of the AUT film were further
estimated using the EIS data obtained in the presence of both
electroactive species immediately after SAM-solution contact.
Sabatini and Rubenstein developed a model for the estimation
of the defects in a SAM based on measurements of the RCT.10
This model assumes that the electron transfer occurs only at
bare spots with planar diffusion to these defective sites. If these
assumptions were correct, the surface coverage (θ) could be
calculated by
θR ) 1 - (RCT /RCT
Au Au/AUT
) (12)
where RCTAu/AUT is the charge-transfer resistance for the SAM
covered electrode, and RCTAu for the unmodified electrode. In
that model, the value of RCT is considered to be strictly a
consequence of the insulating properties of the monolayer. As
it was previously discussed, the mass transport to defective sites
could be affected in such systems by the establishment of
electrostatic interactions at the interface leading to an extra
contribution to RCT that will be positive in the case of repulsive
interactions and negative for the attractive ones. This contribu-
tion will lead to an over- and underestimation, respectively, of
the coverage according to eq 12. The values of RCT and the
corresponding coverage obtained using this approach (θR) in
the presence of [Fe(CN)6]-3 and [Ru(NH3)6]+3 solution species
are given in Table 5. Amatore et al.25 explained that eq 12 must
not be used when the coverage is larger than 0.9. For these
cases, the coverage can be estimated using a model that
considers the defects in the layer as individual microelectrodes
of a specific size and separation distance. At high frequencies,
these microelectrodes show isolated spherical diffusion profiles.
The real Faradaic impedance component can be written as26-28
ZR ) RCT (1 - θ)-1 + σW (1 - θ)-1 ω-1/2 (13)
ZR is linear dependent on ω-1/2 with a slope (m) of σW (1 -
θ)-1. The high-frequency limit is marked by the term RCT (1 -
θ)-1. It is possible to estimate the coverage (θ DS) from the
slope (m) of the ZR versus ω-1/2 plot in the high-frequency
region, as
θDS ) 1 - (σW/m) (14)
where σW is the Warburg impedance coefficient, obtained from
the slope of the ZR versus ω -1/2 plot for the bare Au electrode
in the high frequencies region. Equation 14 is related to the
defects size through the microarray model proposed by Amatore
5360 J. Phys. Chem. C, Vol. 111, No. 14, 2007
Figure 10. Art model explaining the evolution with time of the permeation properties of the AUT film by Ru(NH3)6+3/+2 solution species in KCl
since the first contact electrode-solution. The electrolyte anion binding performs a progressive surface charge neutralization allowing the easier
permeation of the distorted AUT layer.
et al.25 The coverage can be related with these parameters
through the equation
1 - θDS ) (σW/m) ) ra2/rb2 (15)
The term 1- θDS corresponds to the pinhole fraction area in
the SAM, ra is the pinhole radius, and rb is the half distance
between the center of two neighboring pinholes. It is possible
to estimate ra from the frequency value (q) that corresponds to
the turning point between the high and low frequencies region
in the ZR versus ω-1/2 plot using
q ) D/0.36ra2 (16)
D is the diffusion coefficient of the redox species. In addition,
Tokuda et al.57 showed that q can be estimated from the
maximum value in the -Zi versus ω-1/2 plot (ωt) as
ωt ) q/2 (17)
When the ZR versus ω-1/2 plots for the bare electrode in the
presence of both electroactive species in both electrolytes were
plotted, the Warburg coefficients were determined from the slope
of these plots in the high-frequency region. At least 5 indepen-
dent measurements were registered in NaF 0.2 M and averaged.
The values obtained were σW ) 192 Ω cm2 s -1/2 and σW )
100 Ω cm2 s-1/2 in the presence of Fe(CN)6-3 and Ru(NH3)6+3,
respectively. Values of σW ) 127 Ω cm2 s-1/2 and σW ) 126
Ω cm2 s-1/2 were obtained, respectively, in the same way in
KCl 0.2 M. The Warburg coefficients for both electroactive
probes are very close as expected for species with diffusion
coefficient in the same order of magnitude (6 × 10-6 cm2 s-1
for Fe(CN)6-3/-4 29 and 3.84 × 10-6 cm2 s-1 for Ru(NH3)6+3/+2
at 288 K30) and in the same bulk concentration. The values of
m were obtained from the slope of similar plots for the AUT-
modified electrode. Values of m ) 1210 Ω cm2 s-1/2 and m )
21 571 Ω cm2 s-1/2 were obtained, respectively, for hexacy-
anoferrate and hexaamineruthenium species in NaF 0.2 M and
m ) 633 Ω cm2 s-1/2 and m ) 13 316 Ω cm2 s-1/2 in
Campiña et al.
KCl 0.2 M. The maximum in the -Zi versus ω-1/2 plots
allowed the calculation of ωt ) 271 Hz and ωt ) 9 Hz,
respectively, in NaF 0.2 M while ωt ) 74 Hz and ωt ) 29 Hz
were determined in KCl 0.2 M. The coverage and the value of
the parameters ra and rb were estimated from these data using
eqs 14-17 and are shown in Table 5. The values for the
coverage obtained either with the Sabatini and Rubenstein model
in which θR, Fe ) 0.874 and θR, Ru ) 0.999 or with the defects
size model in which θDS, Fe ) 0.841 and θDS, Ru ) 0.995
(both in NaF 0.2 M) have shown to be contradictories and
dependent on the nature of the established interactions. As it
was predicted previously, the results are under- and overesti-
mated due to the unconsidered extra contributions of these
electrostatic interactions on the charge-transfer process (and
therefore on RCT). The microstructure parameters of the mono-
layer were also determined showing the same features. A
monolayer with pinholes defined by a radius of ra ) 1.7 µm
and separated by a distance of 8.8 µm (2rb with rb ) 4.4 µm)
were obtained in the presence of hexacyanoferrate in NaF 0.2
M while for the case of hexaamineruthenium, a pinhole radius
of ra ) 9.6 µm and pinhole separation of 280 µm (rb ) 140
µm) were obtained. Results obtained in KCl 0.2 M were also
dependent on the studied species and showed a still higher value
of pinhole radius in the presence of hexacyanoferrate (3.3 µm).
It can be noticed that the estimation of these parameters is still
more sensitive to the kind of electrostatic interactions than the
coverage. These results must be also taken in a careful way,
although the parameters obtained for the Fe(CN)6-3/-4 pair in
NaF 0.2 M indicated the presence of pinholes of comparable
size and separation distance than those reported for a monolayer
of the shorter 3-mercaptopropionic acid (MPA)24 (ra ) 1.9 µm
and rb ) 11 µm), which is expected to form a much more
disordered structure. The application of these models to the
elucidation of the microstructure of charged SAMs has shown
to constitute a still first and rude approximation. It seems that
the conclusions reached on the basis of the results obtained just
in a situation of repulsive interactions constitute a biased vision
of the system. The development of new models with a pondered
weight of the different effects playing a role in the transfer
Selective Permeation of AUT Monolayers on Au
Figure 11. Topographic AFM images performed in tapping mode for: (A) a bare Au slide, and (B) a 24 h AUT modified Au slide. The scan size
is 1 µm.
mechanism is still necessary for a better characterization of
charged SAMs.
3.4. AFM Imaging. The morphology of the Au surface after
the immersion in AUT was investigated using AFM. Figure 11
shows the images taken for the bare Au (A) and for a 24 h
immersed Au slide in AUT (B). No significant difference in
the topography was observed between the bare and the modified
slides. The root-mean-squared roughness factor obtained from
the topographies of both surfaces resulted in very similar
values: 1.25 nm (bare Au) and 1.19 nm (AUT-modified Au
slide). This observation agrees with the previously reported
behavior for the adsorption of a mercaptosuccinic acid (MSA)
monolayer on Au by M. Chirea et al.38 The building of
alternative poly(L-lisine)/ MSA stabilized Au nanoparticles
layers on a self-assembled MSA monolayer on Au, showed a
strong change in the observed morphology by AFM just after
the first deposited poly(L-lisine) layer. However no significant
difference was found between the topographies corresponding
to an Au/MSA and the bare Au slide. The images obtained seem
to discard the formation of thick and/or heterogeneous AUT
multilayer. The insulating properties observed for the film using
the previous techniques should be associated mainly to the
presence of a relatively homogeneous monolayer of AUT on
surface.
4. Conclusions
The results obtained after the immersion of polycrystalline
Au surfaces in an AUT 1 mM solution in pure ethanol supports
the fast formation of a relatively well-packed, compact and
dynamic (liquidlike) monolayer slightly more disordered than
the quasi-crystalline structures formed by n-alkanethiols on Au
(111). The study of the adsorption kinetics by means of the
QCM technique agreed with a process occurring in 2 stages
consisting on a fast adsorption step that is followed by slower
self-organization that extends until the surface is removed from
the solution and leads to highly ordered structures. AFM
experiments seem to discard the formation of thick multilayers
after 24 h immersion in AUT. CV and EIS experiments
performed for the modified electrodes in supporting electrolyte
showed greatly enhanced capacitive behavior when compared
to the bare Au. The film thickness and tilt chain angle reached
average values of 1.6 nm and 26° in the studied potential region.
The ET processes of highly charged electroactive solution
J. Phys. Chem. C, Vol. 111, No. 14, 2007 5361
species through the AUT layer are governed by the electrostatic
interactions established in the SAM-solution interface between
the charged amino groups and these probe species. A mechanism
of selective ion permeation into the monolayer allowed by the
structure of the film and driven by the electrostatic interactions
explains the facilitated ET observed for the Fe(CN6)-3/-4 anions
(attractive interactions) and the strongly hindered process
obtained for Ru(NH3)6+3/+2 (repulsive interactions). Strong
evidence of negligible desorption of the SAM in the time range
in which the experiments were performed is provided. The role
of pH in the amino-amino self-repulsion, the temperature and
the role of the electrolyte anion (type and concentration) in this
mechanism will be deeply and rigorously investigated in future
work. The fitting of these data to models, which do not consider
the effect of the electrostatic interactions on the nature of these
processes, may lead to contradictory over- and underestimated
results for the structural parameters.
Acknowledgment. This work was supported by the Euro-
pean Union under the network SUSANA (“Supramolecular Self-
Assembly of Interfacial Nanostructures”, contract HPRN-CT-
2002-00198). The authors acknowledge Professor Ana Cristina
Freire (ICETA) for the support and use of the QCM technique.
J.M.C. gratefully acknowledges FCT (Fundação para a Ciência
e a Tecnologia de Portugal) for the concession of a research
grant under the project (SFRH/BD/23851/2005).
Note Added after ASAP Publication. This article was
published ASAP on February 28, 2007. In the fourth paragraph
of section 3.3, the word “insensitive” has been changed to
“sensitive”. The correct version was posted March 7, 2007.
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