Article

pubs.acs.org/JPCC

Effect of Self-Assembled Monolayers on the Locally Electrodeposited

Silver Thin Layers
Roman G. Fedorov and Daniel Mandler*
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel
*
S Supporting Information

ABSTRACT: The localized electrodeposition of silver on gold coated with self-assembled

monolayers (SAMs) by scanning electrochemical microscopy (SECM) is reported. The
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SAMs were ω-functionalized alkanethiols of the form X−(CH2)2SH, X = OH, NH2, CO2H,
SO3H, as well as 4-mercaptobenzoic acid. The SAMs were characterized by X-ray
photoelectron spectroscopy (XPS) and cycling voltammetry (CV). The anodic dissolution
of a Ag microelectrode, which was held within a few microns from the Au surface, formed a
well-controlled flux of Ag+. Deposition of silver nanostructures was driven by the
electrochemical reduction of the Ag+ on the Au surface. The effect of the functional group
on the Ag local deposition was studied and compared with bulk deposition on the same
SAMs. For bulk deposition, we found that the interaction between Ag+ ions and the
functional group of the alkanethiols slowed the kinetics of Ag deposition, shifting the
deposition to potential that is more negative and caused the formation of large, well-faceted
Ag crystals. A clear correlation between the potential shift value and the morphology of
deposited Ag was observed. The local deposition of Ag showed distinct difference
compared to bulk deposition. We found that a continuous and homogeneous Ag film was formed locally below the Ag
microelectrode in the presence of a 3-mercaptopropionic acid monolayer. This was observed when a 120 s delay between the
electrogeneration of the silver ions and the application of a negative potential to the gold surface was applied. Moreover, the
potential applied to the Au surface also affected deposition. The deposited silver was recollected by the Ag microelectrode by
stripping the silver from the Au surface while holding the microelectrode in the same position. This enabled calculating the
thickness of the Ag film deposited on the Au coated with 3-mercaptopropionic acid. Additional experiments clearly indicated that
the mechanism of deposition involved complexation of silver ions by the SAM and their local reduction, which commenced prior
to applying a negative potential to the Au surface.

■ INTRODUCTION
Controlling the morphology, crystal structure, and dispersion of
deposited thin metal layers (particulate or uniform) onto
different substrates (conductors and insulators) plays a major
role in many areas, such as molecular electronics, catalysis,
sensing, electroplating, and many more. The methods of
deposition can be divided into two categories: from the gaseous
phase, e.g., vapor deposition, sputtering, chemical vapor
deposition, and from the solution, such as printing, dip-coating,
and electrochemical deposition. The latter has some distinct
advantages1 including higher deposition rates, avoiding high-
stress deposits, and coating very rough substrates or complex
geometries uniformly. In addition, processing and controlling
are relatively simple, and the equipment is inexpensive.
A convenient and known approach for controlling metal
deposition involves modification of the surface by a very thin
layer, which, on one hand, does not block electron transfer and,
on the other hand, affects the nucleation and growth of the
metal. Such a layer can be formed by the spontaneous
adsorption of self-assembled monolayers (SAMs).2 Numerous
studies have focused on metal deposition onto thiol-based
SAMs. The latter are known to form organized layers and are
quite stable under the application of potential. Such SAMs
enable manipulating the chemical structure of the surface and
therefore control the deposit morphology and properties. The
kinetics and mechanism of electrodeposition can be controlled
by varying the chain length of the alkanethiol. While long
alkanethiols (R−(CH2)nSH, n ≥ 12) tend to completely
suppress charge transfer, short functionalized alkanethiols (n =
2−6) do not avoid electron transfer (that is needed to reduce
the metal ions) and, at the same time, can affect the interactions
between the metal ions and the electrode interface via the
functional group, R.
The deposition of metals on SAMs has been well
documented by several reviews.3 Most of these studies describe
metal deposition from the gaseous phase (usually in vacuum).
This approach is favored due to the relatively simple chemistry
that is involved (in the absence of ligands and interaction with
the solvent), and physical properties are more easily
interpreted. Another significant advantage of deposition from
the gaseous phase is that the clusters can be ionized,
Special Issue: Kohei Uosaki Festschrift
Received: July 12, 2015
Revised: December 14, 2015
Published: January 7, 2016

© 2016 American Chemical Society 15608 DOI: 10.1021/acs.jpcc.5b06680

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accelerated, and filtered by electrical and magnetic fields, and in
analogy to mass spectrometry, specific size selection becomes
possible.3b Finally, in most of these studies it has been shown
that the metal deposits on top of the monolayer due to
favorable interactions with the end group of the SAM.
At the same time, numerous papers report on the
electrodeposition of metals onto SAMs.4 This research also
contains extensive evidence of the effect of SAM functionality
on metal deposition. The careful choice of the functional group
allowed metallization of thin organic layers with foreign metals
and thus the formation of sandwich structures (metal−
organic−metal) for different deposited metals such as Pt,5
Pd,6 Rh,7 and others. On the other hand, in most cases where
the interaction between the deposited metal and the end-group
of the SAM is relatively weak, metal deposition occurs on the
metallic substrate rather than on top of the monolayer. For
example, Ag adsorption and nucleation onto electrodes covered
with functionalized alkanethiols8 occurs at different rates
depending on the nature and polarity of the end groups. It
was found that negatively charged organic molecules (SAMs
terminated with −COO−, −SO3−) possess strong interaction
with silver ions. Nevertheless, the reduction of silver ions leads
to deposition on the Au substrate due to the strong interaction
between the two metals. Furthermore, it was also reported that
thiols with different functional groups form SAMs with different
defect density.8b This clearly plays an important role recalling
that such defects serve as nucleation sites for metal electro-
deposition.
Electronics as well as other fields tend to miniaturization.
Localization of different processes in the micro- and nanoscale
is becoming essential in fabrication. Therefore, developing of
new approaches, which allow performing local deposition of
metals on SAMs, is of great interest to basic and applied
research. During the recent years various methods such as
nanolithography,9 laser-assisted deposition (LAD),10 tip-
induced metal deposition,11 scanning electrochemical micros-
copy (SECM),12 and scanning ion conductance microscopy
(SICM)13 have been developed and continuously improved for
local metal deposition. While in the former three approaches
the local control of the morphology and structure is insufficient,
SECM and SICM enable carrying out various electrochemical
manipulations locally14 and also may provide good control of
deposit morphology. For example, we have shown that by
varying the chain length of alkanethiol SAMs the morphology
of localized Ag deposition could be controlled.15 SECM has
certain advantages over bulk electrochemical deposition
approaches not only in the spatial resolution but also in
morphology control as it enables managing the flux of
electroactive species to the electrode surface and therefore
provides a better control of metal deposition.
The local deposition of metals on SAMs has not been widely
studied (as opposed to the massive work on electrochemical
deposition of metals on SAMs) and represents an almost
pristine area of research. Our aim in this contribution is to
understand the effect of the functional group of the SAM on Ag
local deposition. Specifically, a flux of Ag+ was generated at the
SECM Ag tip (short pulses), while different potentials were
applied to a Au substrate covered with various ω-functionalized
alkanethiol SAMs, i.e., HS(CH2)2X (X = CO2H, NH2, SO3H,
OH) as well as 4-mercaptobenzoic acid. The structure, density,
and molecular orientation of such organic monolayers in
aqueous solution are well documented in the literature.16 We
found that the end group significantly affects the local
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deposition of silver, resulting in morphological changes on
the early stages of the growth process. Thus, different Ag
nanostructures were formed, i.e., uniform and particulate thin
layers, cubes, hexagonal, and elongated prisms and rods. The
comparison of bulk and local Ag deposition reveals interesting
phenomena. The morphology of Ag deposition on carboxyl-
terminated alkanethiol SAM (3-mercaptopropionic acid)
depends not only on the concentration of electrolyte
components and the deposition regime (potential, time) but
also on the configuration of Ag+ flux to the electrode surface.
While Ag cubes were obtained in a conventional three-
electrode cell, a Ag uniform thin layer was formed by SECM.
Furthermore, we found that local Ag deposition occurs even
without applying any external potential to the Au/SAM
electrode. This led us to conclude that the local deposition of
Ag on 3-mercaptopropioinic acid/Au involves complexation of
the silver ions by the functional group followed by metal
reduction independently on the application of potential.
■ EXPERIMENTAL SECTION
Instrumentation. The setup of the homemade SECM was
previously described.12 The vertical resolution was 0.075 μm. A
CHI-750B electrochemical workstation bipotentiostat (CH
Instruments Inc., Austin, TX, USA) was used for the
electrochemical measurements as well as for SECM operation.
High-resolution scanning electron microscopy (HR SEM,
Sirion, FEI Company, USA) equipped with an EDX detector
was used to image the morphology and crystal structures in the
micro and nano range as well as to analyze the composition of
the deposits. For each sample the average size of Ag
nanostructures was determined by image processing using
“ImageJ”.
Chemicals. All chemicals were of analytical grade and used
as received. Cysteamine, 3-mercaptopropionic acid, 2-mercap-
toethanesulfonic acid, 2-mercaptoethanol, 4-mercaptobenzoic
acid, potassium perchlorate (≥99.995%), perchloric acid
(99.999%), silver nitrate (99.99%), hexaamineruthenium(III)
chloride (98%), and potassium nitrate (99.995%) were
obtained from Sigma-Aldrich. Ethanol was purchased from
Merck. All solutions were prepared using deionized water (18.3
MΩ·cm, EasyPure UV, Barnstead). Ru(NH3)6(NO3)3 was
prepared by adding small volumes of saturated KNO3 solution
into a saturated Ru(NH3)6Cl3 solution. This caused the
immediate precipitation of Ru(NH3)6(NO3)3, which was
collected and dried in vacuum.
Procedures. The substrate was thermally evaporated Au
(200 nm thick films, 99.999%, with a thin Cr underlayer) onto
glass plates (Berliner Glass, 1.1 mm thickness). The Au
substrates were cleaned by consecutive baths of deionized water
and ethanol, dried under nitrogen flow, and thermally
annealed.17 Modification of Au substrates was carried out by
immersing the sample into a freshly prepared 3 mM solution of
the alkanethiol in ethanol for 20 min. These solutions were
deaerated for 10 min under Ar flow.
The kinetics of Ag electrochemical deposition on Au/SAM
was studied in a conventional three-electrode cell purged by
argon and equipped with a silver chloride (1 M KCl) reference
electrode and a Pt wire auxiliary electrode. The potentials are
therefore quoted vs the Ag/AgCl (1 M KCl) reference
electrode. Cyclic voltammetry (CV) and chronoamperometry
were employed.
Silver microelectrodes (25 μm diameter) with an RG (ratio
between the diameter of the insulating glass sheath and the
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conducting disc) of ca. 10 were prepared using borosilicate
capillary (Gerner Glass, Germany, ID/OD 1.60 ± 0.05/2.00 ±
0.05 mm) and 25 μm diameter silver wire (99.95% Alfa Aesar,
Lancashire, UK) following a conventional procedure.18 After
preparation the microelectrodes were electrocycled in 0.1 M
H2SO4 and electrochemically characterized by inspecting their
CV in 2 mM Ru(NH3)6(NO3)3 (5 mM KClO4).
The operating principle of SECM has been described
previously.12 Local deposition of silver micro- and nanostruc-
tures has been accomplished in the tip generation/substrate
collection (TG/SC) mode.19 Control over the flux of silver ions
and their reduction was achieved by varying the potentials of
the microelectrode and the substrate independently. Moreover,
we also controlled the time of both pulses, which means that
the application of a negative potential to the gold did not
necessarily start with the application of a positive potential to
the Ag tip. The SECM cell was made of Teflon and consisted of
the silver microelectrode, a Au surface (which was also biased),
a silver chloride (1 M KCl) reference electrode, and a Pt wire as
counter electrode. Controlling the distance between the
microelectrode and the surface was determined by the feedback
mode of SECM using a solution of 2 mM Ru(NH3)6(NO3)3
(Etip = −0.21 V). The tip−surface distance was estimated by
fitting the approaching curve with the theoretical positive
feedback current.20 Once the Ag microelectrode was positioned
a few microns above the surface, an anodic potential pulse
(0.1−50 s) was applied to the Ag tip in KClO4 (5 mM)
solution, generating a flux of silver ions. In some cases, Ag
microelectrode dissolution was performed under potentiody-
namic conditions. These were repeated at different locations
(while maintaining the same distance from the surface) upon
changing the amplitude or the length of the pulse.
The amount of locally deposited Ag was quantitatively
determined based on chronoamperometry whereby the local
deposited Ag was dissolved upon applying a positive potential
to the Au substrate. The tip, which was held close to the surface
(without changing its position after anodically dissolving the
Ag), was biased at negative potential in order to collect the Ag+
ions that diffused from the surface below. The charge that was
measured at the tip was used to determine how much Ag was
initially deposited on the surface. The collection efficiency was
determined by dividing this charge to the initial charge of the
microelectrode that was due to the dissolution of the Ag tip,
after subtracting the charging current that was measured under
conditions where the Ag was not dissolved.
■
RESULTS AND DISCUSSION
Before studying the local deposition of silver on ω-function-
alized alkanethiol self-assembled monolayers (SAMs) by
scanning electrochemical microscopy (SECM) we conducted
a set of experiments in a conventional electrochemical cell and
studied the bulk deposition of Ag at a Au electrode coated with
various SAMs. Furthermore, we characterized also the SAMs on
Au by XPS (see Supporting Information). An evaporated thin
gold film was used as the electrode on which the ω-alkanethiols
were assembled for a given period.
Bulk Ag Electrodeposition. To characterize the system
and determine the working potential window, cyclic voltam-
metry (CV) was performed with different cathodic limits
(Figure 1). The solution contained 2 mM AgNO3, 5 mM
KClO4, and 1 mM HClO4 (pH 3). It can be seen that silver
deposition commences at approximately 0.35 V and is, initially,
kinetically controlled. At more negative potentials the process is
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Figure 1. CV recorded on a bare Au electrode in the presence of 2
mM AgNO3, 1 mM HClO4, and 5 mM KClO4. Scan rate 10 mV/s.
diffusion controlled. On the reverse scan, a stripping
(oxidation) wave appears due to the oxidation and dissolution
of deposited silver. It is evident that the charge under the
oxidation peak is larger than that of the reduction wave, which
is due to the accumulation of the silver on the electrode surface.
The morphology of Ag deposited at 0.3 V for 20 s (Figure 2)
shows a wide range of unshaped nanoparticles without any
preferential structure, which suggests that under these
conditions the growth is not epitaxial. Thus, controlling the
shape and size of the deposited nanoparticles is challenging.
A plausible approach for controlling the morphology and
crystallinity of metal deposition involves the formation of
SAMs. The latter are spontaneously adsorbed on the surface to
form a monolayer, where the ω-functionalized group is heading
toward the electrolyte. We carried detailed analysis of the
organization of the SAMs on Au by XPS (see Supporting
Information). The results show that these relatively short SAMs
adsorb via the thiol group but are not highly organized. The
only monolayer that showed high organization is that of the 4-
mercaptobenzoic acid.
The SAM has therefore two major effects; it can inhibit
electron transfer depending on the length of the carbon chain
and at the same time the functional group can interact with the
metal and its ions affecting nucleation and crystal growth. The
kinetic effect can, in principle, increase the overpotential for
silver reduction and subsequent oxidation. Indeed, the
introduction of short ω-functionalized alkanethiols of the
form X−(CH2)2SH, X = OH, NH2, CO2H, SO3H, and 4-
mercaptobenzoic acid, had a pronounced effect on the CV of
Ag deposition as can be seen in Figure 3. Table 1 summarizes
the potential shift of Ag+ reduction caused by the different
SAMs. The largest shift (94 mV) was observed for 4-
mercaptobenzoic acid. The presence of a phenyl ring, which
is a more significant barrier between discharging the metal ions
and the electrode surface, inhibits electron transfer. In spite of
the small size of the hydroxyl group, a rather large potential
shift of 62 mV was observed for the 2-mercaptoethanol SAM.
We attribute this shift to the relatively strong interaction
between neighboring −OH groups, which, in turn, increases the
tightness of the close-packed organic monolayer. Indeed,
hydrogen bonding of hydrophilic thiol-based SAMs as well as
the formation of a densely packed monolayer structure in the
case of 2-mercaptoethanol are both well documented in the
literature.16a The positively charged amino group of cysteamine
also considerably increases the cathodic overpotential of Ag+
reduction (shift of 49 mV). The charge of the monolayer repels
the positively charged silver ions. The smallest shifts were
observed for 3-mercaptopropionic acid (10 mV) and 2-
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Figure 2. SEM images of Ag bulk electrodeposition on Au from a solution containing 2 mM AgNO3, 1 mM HClO4, and 5 mM KClO4. Deposition
was carried out at 0.3 V for 20 s. Magnifications are 10 000× (A) and 50 000× (B).
Figure 3. CVs of silver reduction−oxidation on bare Au (dash line) and on Au/SAM (solid line) electrodes. The solution contained 2 mM AgNO3, 1
mM HClO4, and 5 mM KClO4. The Au electrode was modified by A − cysteamine, B − 3-mercaptopropionic acid, C − 2-mercaptoethanesulfonic
acid, D − 2-mercaptoethanol, E − 4-mercaptobenzoic acid. Scan rate 10 mV/s.
Table 1. Potential Shift (vs Bare Au) of the Reduction of Ag+
on Gold Caused by Different SAMs (Taken from Figure 3)
monolayer shift/mV
cysteamine 49
3-mercaptopropionic acid 10
2-mercaptoethanesulfonic acid 15
2-mercaptoethanol 62
4-mercaptobenzoic acid 94
mercaptoethanesulfonic acid (15 mV), which possess negatively
charged functional groups and therefore attract the silver ions.
In addition, the formation of a low-density monolayer of 3-
mercaptopropionic acid on the gold surface was reported.16a
Figure 4 shows the effect of the SAM on bulk deposition of
Ag. Clearly, the functional group has a significant influence on
the crystallinity of the deposit. Moreover, we can see that the
concentration of Ag+ affects the shape of the deposit.
Specifically, the presence of cysteamine caused the formation
of scattered hexagonal prisms at 2 mM of Ag+ and elongated
prisms with pointed ends at 10 mM of Ag+. The size of the
crystals varied between 50 and 250 nm for the lower
concentration of Ag+ and between 0.8 and 3.0 μm for the
more concentrated solution. Increasing Ag+ concentration does
not have a structural effect on Ag deposited on other SAMs.
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For example, cubes of different sizes (0.8−1.0 μm and 100−360
nm) were formed on 3-mercaptopropionic acid SAM as a result
of increasing the Ag+ concentration from 2 to 10 mM,
respectively. Elongated prisms, similar to those obtained with
cysteamine, but larger (1.0−7.0 μm) and with lower
distribution density, were formed on the 4-mercaptobenzoic
acid monolayer. Elongated particles (250−500 nm) with flat
upper side were deposited on a 2-mercaptoethanol SAM.
Finally, the presence of a sulfonate-terminated SAM yields a
wide range of unshaped nanoparticles without any preferential
structure. EDX analysis showed that all these nanoobjects are
made of silver.
A distinct correlation between a “large” shift in the potential
(Table 1) and the formation of large crystals (Figure 4) can be
seen. This is expected recalling that the cathodic shift in the CV
is associated with sluggish kinetics.21 Indeed, electrochemical
deposition of Ag on cysteamine, 4-mercaptobenzoic acid, and
2-mercaptoethanol exhibits sluggish kinetics and leads to the
formation of relatively large well-faceted crystals, while in the
case of 2-mercaptoethanesulfonic acid, we did not observe any
morphological effect as compared with a bare Au surface.
However, such an explanation, which is based only on kinetic
aspects, is insufficient and requires a more careful analysis. This
does not explain the case of carboxyl-terminated alkanethiol
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Figure 4. SEM images of Ag bulk deposition on Au(111) modified
with different SAMs. (A and F): cysteamine; (B and G): 3-
mercaptopropionic acid; (C): p-mercaptobenzoic acid; (D): 2-
mercaptoethanol; (E): 2-mercaptoethanesulfonic acid. The deposition
solution contained 2 mM (for A−E) and 10 mM (for F and G)
AgNO3, 1 mM HClO4, and 5 mM KClO4. All deposits were obtained
at 0.30 V for 50 s.
Figure 5. (A) Linear sweep voltammetry (scan rate 10 mV/s) of a Ag microelectrode in 5 mM KClO4 and (B) the potential vs the natural logarithm
of the voltammetry.
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SAM (10 mV shift), which promotes formation of relatively
large cubes.
The shift of the potential observed for the electrochemical
deposition on 3-mercaptopropionic acid is presumably due to
the strong affinity of Ag+ toward carboxylic acids as compared
to the 2-mercaptoethanesulfonic acid. It is worth mentioning
that at the experimental conditions the 3-mercaptopropionic
acid is not charged, while the 2-mercaptoethanesulfonic acid is
negatively charged. The strong complexation of Ag+ by
carboxylic acid monolayers is reported in the literature.8c
Summarizing the results of bulk deposition indicates that the
Ag electrocrystallization and growth mechanism is affected by
the presence and nature of the SAM. Epitaxial well-faceted Ag
clusters are formed (Figure 4) where their shape is clearly
influenced by the end-group of the monolayer oriented toward
the solution. Clearly, such differences, which are shown here,
must be the result of the interaction between the deposited
metal and the functional groups of the SAMs. Previous studies
reported only minor morphological effects, mostly attributed to
the length of the alkyl chain.8a,b We hypothesize that such
interactions lead to the anisotropic crystallographic growth in
the initial stages of Ag electrocrystallization. Further metal
deposition causes only the increase of Ag nanostructures
providing that the process is carried out in the absence of mass-
transport limitations (kinetic control). An important aspect
relates to the place where the metal deposits, whether it is on
top of the SAM or on the Au surface. Taking into account the
short thiols that were employed in this study, which are also
likely to be less organized, implies that Ag deposits on the Au
and not on top of the SAM. This is driven by thermodynamics,
i.e., by the preferred interaction of the silver with the gold
surface. At the same time, the close proximity of the functional
group to the surface is likely to have a stronger influence on the
growth of the crystal.
In this respect, it should be noted that the electrodeposition
of Ag thin layer onto ω-functionalized alkanethiol SAMs was
studied by Kolb and co-workers.8 From analyzing the
underpotential deposition (UPD) of Au on the SAMs they
concluded that the Ag layer favored deposition on the Au
surface due to the strong Ag/Au interaction. Further Ag
overpotential deposition (OPD) may occur either on a
previously deposited Ag monolayer or on top of the SAM,
depending on the length of the alkanethiol chain, the density of
defects in the layer, and the nature of the functional end group,
which in turn may affect the approach of ionic silver species
toward the electrode by complex formation. Hence, employing
short alkanethiol SAMs, which do not tend to form highly
organized arrays (as confirmed by XPS), assures that silver
deposition occurs indeed on the Au surface.
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Figure 6. SEM images of Ag local deposits on Au modified with different SAMs. (A, E) − cysteamine; (B, F) − 3-mercaptopropionic acid; (C) − 4-
mercaptobenzoic acid; (D) − 2-mercaptoethanol (magnification ×100 000). In the right corner of each SEM image is presented an image of lower
magnification (×2500). Deposition was accomplished in two consecutive pulses: first, the microelectrode (positioned 7 μm above the Au/SAM) was
scanned from 0 to 0.38 V at 10 mV/s. An interval of 2 min separated the first and the second pulse, where a potential of −0.18 V was applied to the
Au/SAM for 50 s (A−D). For Au/cysteamine and Au/3-mercaptopropionic acid a potential of −0.3 V was applied to the Au surface (E and F). The
solution consisted of 1 mM HClO4 and 5 mM KClO4.

To address the specific stage of Ag electroreduction
(adsorption, nucleation, growth) whereby the critical changes
happen, namely, the change in the symmetry of the crystal that
is formed, we turned to SECM and the advantages it offers.
Local Ag Electrodeposition. Before carrying out SECM
experiments, it is important to characterize the system and
determine the potential that needs to be applied to the Ag
microelectrode. Figure 5A shows the anodic dissolution of a 25
μm diameter Ag microelectrode in 5 mM KClO4 under
potentiodynamic conditions, conducted in a conventional
three-electrode cell purged by Ar. Dissolution commences at
ca. 0.37 V. Combining the tip current of a microelectrode and
the Nernst equation yields22 a linear dependence between the
applied potential and the natural logarithm of the normalized
current with a slope of 25.5 mV
RT i supra, and varied the potential and time of the potential applied
E = E°′ + ln ∞
F 4aFD
where E°′ is the formal electrode potential; i∞ is the steady-
state diffusion-limited current at the disc microelectrode
positioned far from the substrate surface; a is the electrode
radius; and D is the diffusion coefficient. The slope obtained
(Figure 5B) is ∼31 mV (which was due to obtaining lower
currents than the theoretical values) implies that the electro-
chemical oxidation of the silver microelectrode is close to
reversible. Therefore, we can expect that the current at the
microelectrode will quantitatively reflect the reaction occurring
on the Au surface. This means that the consumption of silver
ions upon reduction on the SAM-coated Au should increase the
current of silver oxidation at the microelectrode, respectively.
It is worth mentioning that we purposely used a relatively
large micrometer size electrode because of two reasons: to
make it easier to locate the deposited structures on the surface
by SEM and to be able to make statistics of the deposited
structures because of depositing many nanoparticles.
The parameters that can be adjusted are the potentials
applied to the tip and the substrate and their duration. We
examined various sequences of pulses where the potential
applied to the tip was always under Nernst conditions, vide
to the substrate. Initially, a potential sweep was applied to the
(1)
silver microelectrode causing its dissolution under potentiody-
namic conditions in the vicinity (7 μm) of the electrode surface.
The second stage involved application of a cathodic over-
potential to the Au/SAM electrode. Interestingly, we found that
better results, vide inf ra, are obtained if the potential applied to
the Au surface is not applied simultaneously with that applied
to the microelectrode, but there is a lag between them. Hence,
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Figure 7. Current transients recorded at the Ag microelectrode. (A) − Generation of Ag+ upon scanning the microelectrode from 0 to 0.38 V and
scan rate of 10 mV/s. (B) − Reduction of silver ions, which were initially deposited on the large Au surface and redissolved. A potential of 0.1 V was
applied to the microelectrode after dissolution as described in A and deposition on the Au surface at potentials of −0.18 (blue curve) and −0.3 V
(black curve) and without deposition of Ag (red curve).
the second potential causes the electrochemical reduction of
both the ions that remained in the gap between the
microelectrode and the Au surface and adsorbed silver ions.
Optimum conditions were obtained for a 2 min interval
between the potential applied to the tip and that applied to the
Au\SAM surface. This time interval was required for removing
excess of Ag+ in the volume between the tip and the substrate.
In addition, it provided sufficient time for the Ag+ ions to
interact with the functional end groups of the SAMs. The
microelectrode was withdrawn from the surface prior to the
second pulse to eliminate its interference with electro-
deposition. Hence, this sequence of pulses caused primarily
the previously adsorbed Ag+ ions on the SAMs to undergo
electrochemical reduction. We found that potentiodynamic
conditions in the first pulse gave better results than applying
potentiostatic conditions, presumably due to the more gentle
generation of the Ag+ flux. The potential sweep at the tip was
stopped automatically when the current reached the desired
value of ca. 20−30 nA. It should be noted that the silver
microelectrode tends to oxidize easily, which affects signifi-
cantly the oxidation currents. Therefore, special care and
pretreatment were necessary to obtain reproducible results.
Furthermore, we could not completely exclude oxygen from the
SECM cell, which also caused some difference between the
potentials applied in the bulk deposition of silver as compared
to these experiments.
Figure 6 shows the effect of SAM on Ag local deposition.
The inset shows the deposit in a lower magnification. It can be
seen that in all cases a well-defined deposit in a disk shape is
formed. The diameter of the disk matches well with that of the
metallic part of the microelectrode, i.e., 25 μm. Electro-
deposition is expected to occur in pinholes and other defects,
e.g., grain boundaries, which reduces the kinetic barrier toward
electron transfer. Indeed, such behavior was reported by us for
thicker films.15 Yet, since fairly short SAMs were employed,
which do not inhibit significantly electron transfer, we expected
that deposition will not be limited to defects but will take place
on the entire surface to which Ag+ ions reached. At the same
time, it can be seen (Figure 6) that the morphology of locally
deposited Ag is considerably governed by the functional group
of the SAM. Nevertheless, the Au/SAM potential and the
distance between the tip and the surface also affect significantly
the morphology of the deposit. Specifically, the presence of
cysteamine caused the formation of Ag flat islands at −0.18 V,
which grew laterally and merged with time (Figure 6A). At
increased cathodic overpotential (−0.3 V, Figure 6E), the two-
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dimensional growth changes into three-dimensional, and the
formation of rod-shaped particles along with other roundish
structures is observed.
The presence of 3-mercaptopropionic acid SAM resulted in
the remarkable formation of a uniform epitaxial layer at −0.18
V (Figure 6B). The layer is made of clear grains that are
separated by grain boundaries. Interestingly, the application of
more negative potential (Figure 6F) yielded similar epitaxial
growth, however, that is 3D. To gain better understanding of
such epitaxial deposition, the quantitative analysis based on
measuring the electric charges (Figure 7) was carried out (see
Experimental section). Specifically, after depositing Ag locally
on the modified Au surface, the microelectrode was kept at the
same position, and a positive potential was applied to the Au
surface. This caused the dissolution of the locally deposited Ag,
which was collected at the microelectrode to which a
sufficiently negative potential (0.1 V) was applied.
We calculated the efficiency of Ag deposition on the Au/
SAM surface. This was accomplished by applying a positive
potential to the electrode surface (after deposition of the silver
locally) and 0.1 V to the Ag microelectrode, which caused the
collection (deposition) of the silver ions generated by
dissolving the predeposited silver disk, at the microelectrode.
Comparing the charge of the reoxidized Ag+ deposited at the
tip (Figure 7B), divided by the initial charge of Ag dissolution
at the same electrode (Figure 7A), gives the collection
efficiency. The latter enables us to determine the thickness of
the deposited film providing that the area of the deposit is
known and assuming homogeneous deposition. Furthermore, it
indicates how much of the electrochemically generated silver
ions are entrapped on the surface, which is clearly a function of
the tip−surface distance and the potential applied to the gold
surface. We found a collection efficiency of 28 ± 3% and 89 ±
9%, for the case of applying a potential of −0.18 and −0.30 V to
the gold surface covered by 3-mercaptopropionic acid,
respectively. Clearly, the different efficiency is due to the
potential applied to the gold surface. We can assume that the
collection efficiency of Ag+ ions on the modified gold surface at
sufficiently negative potential, i.e., −0.30 V, was 100% due to
the following: (a) the potential on the surface was negative
enough so that the deposition was diffusion-controlled, (b) the
gap between the microelectrode and the surface was ca. 7 μm,
which did not allow much of the generated silver ions to diffuse
away from this thin layer cell, (c) the time that the potential
was applied to the gold surface was much longer than the
potential applied to the tip that generated the Ag+ flux, and (d)
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J. Phys. Chem. C 2016, 120, 15608−15617
The Journal of Physical Chemistry C
Figure 8. SEM images of Ag local electroless deposits on a Au modified with 3-mercaptopropionic acid, obtained at different distances between the
tip and the substrate: (A) − 15 μm, (B) − 9 μm, (C) − 3 μm. Ag microelectrode dissolution was performed in potentiodynamic mode. Scan rate was
10 mV/s, and anodic limit was 0.38 V. Magnification is ×100 000.
The area of the collector, i.e., the gold surface, was much larger
than that of the generator, namely, the tip. Therefore, we
believe that obtaining 89% for −0.30 V was because of the
collection efficiency of the tip, which was unable to collect all
the silver ions generated from the gold surface in the patterned
dissolution experiments.
From the charges measured at the tip while collecting the
silver ions we were able to estimate the thickness of Ag
deposited locally on the gold surface. We obtained a thickness
of approximately 23 ± 3 and 74 ± 8 nm, for deposition
potential of −0.18 and −0.30 V, respectively. The thickness of
the Ag deposit is clearly much more than a monolayer as is also
evidenced by the SEM images (Figure 6B and 6F). This is quite
surprising taking into account the large time gap of 2 min,
between the dissolution process at the tip and the deposition of
Ag on the modified Au surface. We attribute it to the thin layer
cell configuration, which almost completely eliminates the
lateral diffusion of the Ag+ ions that are entrapped between the
tip and the surface. The application of negative potential
determines how many of these ions eventually are deposited.
The difference between the deposit at −0.18 and −0.30 V can
be explained by the kinetics of deposition, which seems to
involve a 2D process at less negative potentials and a 3D
process under diffusion-controlled conditions.
Evidently, the SAM on the Au surface has a pronounced
effect in addition to the potential. Comparing the deposits with
a 2-cysteamine vs 3-mercaptopropionic acid clearly shows that
the interaction with the monolayers dictates the structure of the
deposit. The positively charged cysteamine slows the
deposition process and causes the formation of large crystals
at negative potentials, while the favored interaction between the
carboxylic groups and Ag+ results in flat and homogeneous
nanocrystallites.
This is further demonstrated with other SAMs as shown in
Figure 6C and 6D. Ag nanorods along with roundish particles
were formed at −0.18 V on a Au electrode covered with 4-
mercaptobenzoic acid (Figure 6C), while the presence of 2-
mercaptoethanol caused deposition of elongated Ag nanostruc-
tures under the same conditions (Figure 6D).
The most interesting comparison between bulk and local
deposition by SECM (Figures 4 and 6) comprised a 3-
mercaptopropionic acid SAM. The difference is remarkable;
while the former resulted in cubes, the latter formed a
continuous (uniform or particulate) layer. This cannot be
explained by a concentration effect as different fluxes generated
in bulk deposition (Figure 4) affected the size and distribution
of the cubes but not their shape. Such cubes were previously
reported for the electrochemical deposition of silver on
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carboxyl-terminated alkanethiol SAM.15 However, the forma-
tion of a continuous thin layer beneath the Ag microelectrode is
evidently the most exciting observation, as this has never been
reported before for Ag deposition. 3-Mercaptopropionic acid
forms a low-density monolayer on gold, which does not block
electron transfer and is capable of Ag+ complexation. Our
results clearly show that this monolayer allows the electroless
deposition of Ag, which is strongly affected by the distance
between the microelectrode and the substrate as is shown in
Figure 8. The latter shows the electroless deposition of Ag by
pulsing the microelectrode at different distances above the 3-
mercaptopropionic acid/Au. The gold surface was not
connected to an external power supply, yet clear deposition
of Ag is seen for the different distances. Silver was not
deposited under the same conditions without the monolayer.
This implies that the monolayer serves as the complexation site
and captures the silver ions that undergo further reduction on
the surface. The fact that the size and distribution of the
nanocrystallites of Ag are affected by the distance between the
tip and the substrate implies that silver is reduced on the SAM/
Au surface.
In light of the above, we can summarize that the interaction
between the end group of alkanethiol and Ag+ ions is the main
factor explaining the difference in the morphology of silver
nanostructures deposited on different SAMs. This interaction
includes electrostatic coupling of Ag+ ions with charged
functional group of the SAM, adsorption/chemisorption,
complexation process, and even electroless reduction of metal
ions. The functional group can repel (in the case of cysteine) or
attract the metal ions, which will affect the distribution of the
deposit and its structure. It can interact more strongly with the
ions such as in the case of the 3-mercaptopropionic acid. As
long as it does not block electron transfer, the metal will
deposit preferably on the Au surface below the monolayer. The
potential applied to the surface will control whether the growth
is 2 or 3D. Yet, it is still too early to combine all these factors
and the external parameters, i.e., sequence of potentials of the
tip and the surface, in a very clear recipe that can predict clearly
the structure of the local deposit.
■
CONCLUSIONS
The electrodeposition of anisotropic Ag nanoobjects on the
gold surface covered with functionalized alkanethiol self-
assembled monolayers has been accomplished using scanning
electrochemical microscopy (SECM). The process involved
tuning carefully the anodic dissolution of a Ag microelectrode
close to a biased Au/SAM surface and subsequent reduction of
adsorbed silver ions under well-controlled conditions. The
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The Journal of Physical Chemistry C
short chain SAMs that were employed do not form a highly
organized layer and therefore do not prevent Ag deposition on
the Au surface. We found that the end group had a pronounced
effect on the local deposition of silver, resulting in
morphological changes on the early stages of the growth
process. This was attributed to the interaction between Ag+
ions and the functional group of the SAM. Such interaction,
depending on the given functional group, comprises adsorption,
complexation, and even reduction (in the case of 3-
mercaptopropionic acid) of Ag+ ions. Moreover, the effect of
other experimental parameters (electrode potential, composi-
tion of solution, distance between the microelectrode and
surface) on the Ag electrodeposition morphology was also
studied. Thus, different Ag nanostructures were formed, i.e.,
uniform and particulate thin layers, cubes, and hexagonal and
elongated prisms and rods.
The resolution and scope of the deposited structures can be
discussed in two levels. Clearly, the patterns that were formed
and that are in the micrometer scale can be scaled down by
orders of magnitude and depend on the size of the tip.
Nanotips can readily be formed, which will cause the deposition
of nanocrystal patterns in a much smaller area. On the other
hand, the size and aspect ratio of the individual nanoparticles
depend on the growing parameters. These have not been
optimized and are subject to further research. Moreover, the
very special geometry that is formed upon approaching the
surface with a truncated tip, namely, a thin-layer cell, is essential
in confining the metallic species in space and time that allows
their further reduction on the surface. This is unique to SECM.
Interestingly, we found that, generally, the morphology of Ag
deposition on modified Au/SAM electrodes significantly
changes upon switching from bulk to localized (SECM)
processes. This was attributed to the essential difference in
the configuration of Ag+ flux to the electrode surface. The latter
can be accurately controlled in the SECM experiment by
varying the potential of the microelectrode dissolution as well
as the distance between the tip and the substrate. The most
exciting comparison between bulk and local Ag deposition
comprised 3-mercaptopropionic acid SAM, which enabled
complexation and even reduction of Ag+ ions without applying
electric potential. Ag cubes and a continuous (uniform or
particulate) Ag layer were formed in bulk and local electro-
deposition, respectively. The thickness of such a uniform flat
layer was estimated by chronoamperometric measurements.
Hence, not only is the scope of the method very wide, which
suggests that numerous systems can be studied similarly, but
also the uniqueness of this approach makes it very interesting
with respect to the rules that dictate the structure of localized
deposits in the presence of self-assembled monolayers.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.5b06680.
Characterization of the SAMs by XPS (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: daniel.mandler@mail.huji.ac.il. Fax: +972 2 658 5319.
Tel.: + 972 2 658 5831.
Notes
The authors declare no competing financial interest.
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Article
■ ACKNOWLEDGMENTS
The Harvey M. Krueger Family Center for Nanoscience and
Nanotechnology of the Hebrew University is acknowledged.
This project was partially supported by the Israel Science
Foundation (1150/11) and by the Focal Technology Area
through the Israel National Nanotechnology Initiative (INNI).
We would like to express our sincere gratitude to Dr. A.
Vaskevich and Prof. N. Eliaz for the helpful discussion.
■
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15617 DOI: 10.1021/acs.jpcc.5b06680

J. Phys. Chem. C 2016, 120, 15608−15617