Electrochemistry Communications 44 (2014) 19–22

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Short communication

Metal deposition via electroless surface limited redox replacement

S. Ambrozik a, B. Rawlings b, N. Vasiljevic b, N. Dimitrov a,⁎
a
Department of Chemistry, SUNY at Binghamton, Binghamton, NY 13902-6000, USA
b
School of Physics, H.H. Wills Physics Laboratory, University of Bristol, Bristol BS8 1TL, UK

a r t i c l e i n f o a b s t r a c t

Article history: The development of electroless SLRR (ESLRR) utilizing a galvanic cell configuration is demonstrated at a proof-of
Received 13 March 2014 concept level by the deposition of epitaxial Ag layers on Au. ESLRR is realized via the connection and subsequent
Received in revised form 3 April 2014 disconnection of an Au working electrode (WE) to a Pb “executive” electrode (EE). The connection leads to the
Accepted 7 April 2014
underpotential deposition of a Pb monolayer at the WE driven by the stripping of an equivalent amount of Pb
Available online 18 April 2014
from the EE. The disconnection then enables the galvanic displacement of the Pb monolayer by Ag. Electrochem-
Keywords:
ical and in-situ STM characterizations of deposited Ag films show high-quality 2D-growth with no roughness
Electroless SLRR development for up to 50 ESLRR cycles. This approach can be extended to a variety of metal-substrate pairs wide-
Deposition ly applicable in electrocatalysis and energy applications.
Thin films © 2014 Elsevier B.V. All rights reserved.
Galvanic couple
Catalysis

1. Introduction
The deposition of smooth continuous thin metal films is an area of
wide interest for academic and industrial applications. Thin films
allow for unique properties of metals that differ from the bulk to be
exploited as well as device cost minimization. One of the dominant ob-
jectives driving the thin film deposition field is the development of low
cost high activity, typically Pt-based, fuel cell catalysts [1]. The deposi-
tion of such thin films has not been trivial. Conventional overpotential
deposition (OPD) of Pt has illustrated a tendency to nucleate and grow
in three dimensional clusters [2,3]. Overcoming this tendency Uosaki
et al. have shown the growth of continuous 2D thin films via OPD, how-
ever at a very slow deposition rate, 4 ML per hour [4]. Surface limited
redox replacement (SLRR) is a technique that has been developed to
overcome many of the hindrances faced by OPD, and has seen many ap-
plications in the synthesis of high activity fuel cell catalysts with low Pt
loading [5,6]. Introduced by Brankovic et al. [7], SLRR utilizes the mono-
layer limited nature of underpotential deposition (UPD) of a sacrificial
metal coupled with a subsequent galvanic displacement of that layer
by a more noble metal of interest. To date SLRR has been applied to
the realization of monolayer Pt coatings on a variety of metals and
alloy nanoparticles [1] and to the deposition of epitaxial films of Ag,
Cu, Au, Pt, Ru, and Pd on noble metal substrates [7–13].
Conventionally SLRR has been carried out through a multiple im-
mersion approach [7,8] flow cell set-up [10,13,14] and more recently
in a one-cell approach developed by our group [9]. The one-cell
⁎ Corresponding author. Tel.: +1 607 777 4271.
E-mail address: dimitrov@binghamton.edu (N. Dimitrov).
approach has been effectively applied to the growth of Cu [9], Ag [8],
Au [11], and Pt [12,15]. Traditionally SLRR utilizes the application of a
potential by an external source (i.e. potentiostat) in order to realize
the formation of the UPD sacrificial layer (SL) [7–13], and subsequent
open circuit displacement of the SL [9]. However, recent scaling of
SLRR up to the production of industrial quantities of state-of-the-art cat-
alysts renders this protocol energy intensive and difficult to implement
without the use of a high-power potentiostat/rectifier. To that end, al-
ternative approaches relying on less energy intensive scenarios might
be beneficial with ease of application and cost effectiveness. Recently,
a couple fundamental [16] and applied reports [17] discuss aspects of
electroless generation of UPD SL that in turn could lead to the realization
of controlled metal deposition without the use of an external power
source. Herein the utilization of an electroless SLRR (ESLRR) protocol
employing a galvanic couple instead of an external source to power
the SL formation has been explored. The growth of Ag on Au with
underpotentialy deposited Pb (PbUPD) used as sacrificial metal [7,8] is
chosen to reveal the fundamental concept and illustrate at a proof-of-
concept level the feasibility of the proposed approach for ultrathin
film growth.
More specifically, the PbUPD SL on the Au working electrode (WE) is
realized by a short-term contact (in short) with a Pb “executive” elec-
trode (EE) that in a conventional three-electrode cell would be the
counter electrode (CE). The galvanic couple realized upon this contact
enables the application of a kinetically controlled potential on the Au
electrode that is slightly positive of the Pb/Pb2+ reversible potential.
This potential allows for the formation of a full PbUPD layer on the Au
surface powered by the oxidation of equivalent amount of elemental
Pb from the EE. Disconnection of the short activates SLRR that, proceeds
as usual in one-cell configuration, closing the loop for controlled

http://dx.doi.org/10.1016/j.elecom.2014.04.005
1388-2481/© 2014 Elsevier B.V. All rights reserved.
20 S. Ambrozik et al. / Electrochemistry Communications 44 (2014) 19–22
growth, thus completing a cycle of Ag layer deposition without the ex-
ternal power.
2. Materials and methods
Polycrystalline Au (d = 0.6 cm) and Au(111) (d = 0.9) disks of 2 mm
thickness were used as WE. Prior to use each was mechanically polished
to 1 μm using alumina slurry (Buehler) and then electropolished follow-
ing a procedure described elsewhere [11]. After annealing to “red-hot” in
propane flame and cooling in N2 atmosphere the electrode was im-
mersed in a three electrode cell in a “hanging meniscus” configuration
[11]. The solution used for ESLRR of Pb by Ag consisted of 0.1 M NaClO4
(Sigma, 99.95%), 0.01 M HClO4 (GFS Chemical, 70% redistilled), 0.001 M
Pb(ClO4)2 (Aldrich, 99.995%), and 0.0005 M AgClO4 (GFS Chemicals,
99.999%). All solutions were made using Barnstead Nanopure® water
and high-purity grade chemicals as received from the vendors. Prior to
use all solutions were thoroughly deoxygenated with ultrapure N2 for
at least 30 min.
In the growth studies a Pb wire was used as EE (instead of CE) and
was isolated in a glass tube (with 6–8 μm separator membrane) con-
taining identical solution to the one of the growth cell excluding Ag
ions. All potentials in the paper (unless otherwise noted) are reported
versus a mercury-mercurous sulfate electrode (MSE). The growth pro-
cess was automated utilizing a setup and protocol described elsewhere
[11,12]. However, instead of using potentiostat, the WE and EE were
connected in short for 1 s. Characterization of deposited Ag films was
carried out by cyclic voltammetry of PbUPD and Ag stripping experi-
ments in a solution of 0.1 M NaClO4, 0.01 M HClO4 and 0.001 M
Pb(ClO4)2. All electrochemical characterization experiments were per-
formed by CH Instruments, model 400a potentiostat and its coupled
software. Also, Pt wire was used as CE.
STM characterization was performed in situ with an Agilent 4500
SPM microscope, using 2100 Controller and Pico Scan software in solu-
tion where the potential control was provided by Agilent 300S Pico bi-
potentiostat. Tips for the STM experiments were electrochemically
etched in 1.6 M CaCl2 from Pt0.9Ir0.1 wire using an AC voltage of 25–30
V and subsequently insulated with Apiezon wax.
3. Results and discussion
In order to illustrate the potential realized between the WE and EE
upon connection a mixed potential diagram is provided in Fig. 1A.
Under the assumption of O2-free environment, this diagram clearly
shows that the anodic current of Pb oxidation (EE) and the cathodic
Fig. 1. A. Mixed potential diagram illustrating potential, Emix upon realization of Ag–Pb galvanic couple. Ag reduction on Au (blue) and Pb oxidation (red) carried out separately at a sweep
rate of 1 mV s−1. Inset: Same plot in the entire potential range. B. Potential transient of ESLRR deposition of Ag on Au (poly).
current of Ag reduction (on WE) become equal in magnitude (absolute
values used for clarity) at the galvanic couple potential generated by
connecting in short both electrodes [18]. With the Pb oxidation exhibiting
a Butler–Volmer behavior and the Ag reduction being governed by diffu-
sion limitations, the resultant potential should be about 30 mV positive of
the Pb/Pb2+ reversible potential of (~−0.870 V). This potential is nega-
tive enough (see PbUPD potential ranges on both Ag and Au in Fig. 1A,
inset) to result in the formation of a complete PbUPD layer on the WE,
powered by the dissolution of equivalent amount of Pb from the EE.
Potential transients of replacement events showing uninterrupted
potential control are seen in Fig. 1B. It can be clearly seen that the exec-
utive electrode applies a relatively consistent potential. Also, no poten-
tial drift associated with possible transformation of the executive
electrode could be seen. The potential applied is in satisfactory agree-
ment with that predicted via the mixed potential diagram. More flexi-
bility in the potential control could be achieved by manipulating the
oxidative kinetics of EE. The analysis of the transients presented in
Fig. 1B suggests almost identical exchange behavior in the growth of
Ag via ESLRR with that exhibited during the course of conventional
SLRR deposition [8].
In order to quantitatively determine the amount of Ag deposited
with each cycle, stripping of accordingly grown layers was performed
by anodic potential scans. The stripping curves are presented in Fig. 2
along with an inset showing the relationship of charge vs. the number
of ESLRR events. It can be seen that the expected dependence features
a coarse linear trend showing between 1.5 and 1.8 ML of deposited Ag
per SLRR event; this is slightly higher than that expected of 1.6 ML
based solely on the charge of a Pb UPD ML [7,8]. The morphology of
ESLRR grown films and their stripping were characterized by in situ
STM. A Ag film deposited by 5 ESLRR events on Au(111) is shown in
Fig. 2 (left inset) at a potential of 0.250 V (Pb/Pb2+). It can be observed
that the deposit features a morphology typical for SLRR growth entailing
homogeneous island nucleation followed by island coalescence upon
multiple SLRR cycles [8,9,11]. The Ag was subsequently stripped and
the image taken at 1.0 V (Pb/Pb2+) following stripping is presented in
Fig. 2 (right inset). This figure shows the disappearance of large islands
and the morphology characteristic of Au bulk-terminated surface
consisting of monatomic steps and large terraces. The remainder of
small uniform islands can be attributed to a partial Ag UPD layer present
at this potential as illustrated by Garcia et al. [19].
Following a single ESLRR event the electrochemical behavior of the
deposit coincides with that of bulk Ag (Fig. 3A). This is in agreement
with findings of Pauling et al. [20] on the screening effect of UPD metals.
Additional insight on this is obtained by the in situ STM insets presented
 S. Ambrozik et al. / Electrochemistry Communications 44 (2014) 19–22 21

Fig. 2. Ag stripping curves following different number of ESLRR events (sweep rate: 1 mV s−1). Inset, plot: Relationship between number of replacements and stripping charge. Inset, STM-
left: Ag layer after 5 ESLRR events. Inset, STM-right: Au surface after stripping of the Ag layer.

in Fig. 3A showing the well-defined, bare Au(111) surface prior the Ag
growth. A single ESLRR event leads to the deposition of Ag film of
more than a monolayer thickness as evidenced by clustered appearance
of the deposit. The obtained morphology is nearly identical with that
reported previously for one conventional SLRR event [8,11].
The negligible roughness evolution with the number of ESLRR
events can be seen in Fig. 3B where the active area of the deposit is doc-
umented quantitatively by the PbUPD charge, for up to 50 ESLRR events.
The results show excellent agreement with results previously reported
by Vasilic et al. [8]. This further illustrates and confirms the ability of
presented potentiostat-free approach to effectively reproduce results
previously reported by the conventional SLRR protocol.
4. Conclusions
This paper demonstrates at a proof of concept level the application of
SLRR thin film deposition without coupling to an external power source.
In the newly proposed ESLRR approach a Pb electrode was connected to
the working electrode in order to drive the formation of a PbUPD layer on
the working electrode by the stripping of an equivalent amount of Pb

Fig. 3. A. PbUPD on Au (red curve) and on Ag deposited on Au by one ESLRR event. Inset, top: Original Au(111) surface. Inset, bottom: Ag deposited on Au(111) by one ESLRR event. B. PbUPD
on Ag deposited on Au(111) by different number of ESLRR events; sweep rate: 20 mV s−1.
22 S. Ambrozik et al. / Electrochemistry Communications 44 (2014) 19–22
from its surface. The Pb electrode is subsequently disconnected to en-
able a typical SLRR event. This purely electroless deposition method al-
lows for perfectly controlled growth which may be repeated to form
multiple layers. The proposed approach successfully reproduces previ-
ously reported results by conventional SLRR and constitutes a feasible
option for straight forward and cost-effective thin film deposition in a
variety of metal-substrate pairs at an industrial scale of operations.
Acknowledgments
The authors of this work acknowledge the financial support of the
National Science Foundation, under contracts DMR-CAREER-0742016
and CHE-1310297. N.V. and B.R. acknowledge the support of the Bristol
Center for Nanoscale and Quantum Information. The help of Dr. Stoyan
Bliznakov in the development of ESLRR setup is highly appreciated.
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