13614

J. Phys. Chem. C 2010, 114, 1361413619

Fabrication and Wettability of Nanoporous Silver Film on Copper from Choline

Chloride-Based Deep Eutectic Solvents
C. D. Gu,* X. J. Xu, and J. P. Tu
Department of Materials Science and Engineering, State Key Laboratory of Silicon Materials,
Zhejiang UniVersity, Hangzhou 310027, China
ReceiVed: June 6, 2010; ReVised Manuscript ReceiVed: June 30, 2010

Nanoporous Ag films on copper alloy substrates were fabricated by the galvanic replacement reaction from
the choline chloride-based deep eutectic solvents (DES) containing AgCl. It was found that the morphologies
of the films were largely dependent on AgCl concentrations and plating temperatures. Interestingly, selfassembled nanoporous network of Ag films with ligament and channel width in the range of 20-80 nm was
formed on the copper alloy substrate from 0.01 M AgCl DES solution either at room temperature or at 50 C.
The as-deposited porous Ag films exhibited hydrophilic properties. On the contrary, after surface modification
by a monolayer of n-dodecanethiol, the contact angle of porous Ag film increased largely with plating times,
and a superhydrophobic surface was finally obtained with a contact angle of 160 ( 1. Wenzel and
Cassie-Baxter models were used to qualitatively illustrate the importance of the surface roughness of the Ag
films to the wetting property.
1. Introduction
Intensive research efforts are currently focused on the
fabrication of superhydrophobic surfaces because of their
significance in both fundamental research and practical applications, including water-repellent coatings, self-cleaning surfaces,
and low-drag microfluidics.1-5 Superhydrophobic surfaces,
inspired by some plants leaves and insects shells, share two
common features: they are made of (or covered by) hydrophobic
materials, and the surfaces are not flat at the micro/nanometer
scales but have micro/nanobinary structures.1-5 Galvanic cell
reaction has been used extensively for producing micro/
nanobinary structures with hydrophobic and superhydrophobic
surfaces because of its facile operation and low cost.2,6,7 Copper
and copper alloys are important engineering metallic materials,
which have been attracting intensive interest to be used as
superhydrophobic substrates.7-18 Micro/nanobinary structure of
silver films on copper and copper alloys was fabricated by
galvanic exchange reactions from the aqueous AgNO3 solution.6
However, the micro/nanobinary structured silver films usually
exhibit hydrophilic property with contact angles less than 50.6
With the further surface modification process by coating low
surface energy materials, such as stearic acid7 and n-dodecanethiol,2,6 the Ag surface was turned from hydrophilicity to
hydrophobicity.
Room-temperature ionic liquids are superior media for the
electrodeposition of metals and semiconductors and have an
unprecedented potential to revolutionize electroplating because
of their wide electrochemical windows, extremely low vapor
pressures, and numerous, only partly understood, cation/anion
effects.19 Abbott et al. first described the applications of a
relatively new class of ionic liquid on the basis of eutectic
mixtures of choline chloride (ChCl) with a hydrogen bond donor
species, which is named as deep eutectic solvents (DESs).20
Moreover, unlike the conventional ionic liquids, DESs can be
* To whom correspondence should be addressed. E-mail:
changdong_gu@hotmail.com. Phone: +86 571 87952573. Fax: +86 571
87952856.

easily prepared at low cost and with high purity. DESs are
promising solvents used for the deposition of a range of metal
coatings including Zn,21 Cr,22 and Cu23 at high current efficiency
and also for metal dissolution processes such as electropolishing.24,25 Recently, Abbott et al. demonstrated that porous
metallic silver films can be obtained by electroless deposition
from the ChCl-based ionic liquid.26,27 However, the question
of whether the porous Ag films from ionic liquids are hydrophobic or hydrophilic has not been explored. In our opinion,
the pores and channels in the silver deposit make the silver
surface rough with nanostructures, which could confer a
potential hydrophobic property to the surface.
In this study, porous Ag films on copper alloy substrates with
different surface morphologies were fabricated by the galvanic
replacement reaction from the DES solution containing ChCl
and ethylene glycol (EG) eutectic mixtures. Surface topography
and crystal structure of these films were characterized by
scanning electron microscope (SEM) and X-ray diffractometer
(XRD), respectively. The wettability of these surfaces was
extensively investigated through measuring the contact angle
(CA) of water.
2. Experimental Section
2.1. Fabrication of Porous Ag Films on Cu Alloys. ChCl
(AR, Aladdin) and ethylene glycol (EG) (AR, Aladdin) were
used as received. The DES was prepared according to ref 28,
which was formed by stirring the two components in a mole
ratio of 1ChCl:2EG at 75 C until a homogeneous colorless
liquid was formed. The used substrate was a commercially
available and industry widely used copper alloy foil (cold-rolled
alloy C194). Alloy C194 has a nominal composition of 2.4%
iron, 0.03% phosphorus, and 0.1% zinc with the balance of
copper. A surface cleaning treatment of the copper alloy
substrate was conducted to remove the industrial oil from the
surface by electrolytic degreasing and deionized water rinsing.
Before the plating process, the substrate was dried with flowing
air. Porous Ag films on the Cu alloys were obtained by facilely
immersing the cleaned copper alloy foils into 0.01 or 0.1 M

10.1021/jp105182y 2010 American Chemical Society

Published on Web 07/22/2010

Fabrication of Nanoporous Silver Film on Copper

J. Phys. Chem. C, Vol. 114, No. 32, 2010 13615

Figure 1. Surface morphologies of as-deposited Ag films on Cu alloys from 0.01 M AgCl DES solution at RT, where the insets are the corresponding
high resolution images. The deposition time is (a) 1, (b) 5, and (c) 10 min. (d) The EDS mapping analysis corresponding to c. The peaks of Cu and
Fe in Figure 1d are from the Cu alloy substrate.

AgCl (99.8%, Aladdin) DES solution without stirring at room

temperature (RT, 22 ( 2 C) or at 50 C. After a certain
deposition time, the samples were sequentially rinsed with
dichloromethane and methanol.
Suface modification of the as-prepared silver surfaces was
performed by immersing the silver film/substrate in an ethanol
solution of n-dodecanethiol (1 10-3 M) for about 20 h, then
by washing with ethanol and water, and finally by drying with
air.
2.2. Characterization. Structure and morphology of asdeposited silver films were investigated by X-ray diffraction
(XRD, PANalytical XPert PRO diffractometer and Cu KR
radiation ( ) 1.54056 )) and by field emission scanning
electron microscopy (FESEM, Hitachi S-4800), respectively.
Chemical compositions were analyzed with an energy-dispersive
X-ray spectrometer (EDS) attached to the SEM. CA measurements were carried out by using a commercial instrument
(SL200B, Solon Tech., Shanghai). The indicator drop images
were stored via a monochrome video camera by using a PCbased control acquisition and data process. DI water droplets
each having a volume of 1 L were used in the wetting tests.
The static CA values presented in the text were reproducible
within (1 unless otherwise stated.
3. Results and Discussion
Because of the thermodynamics of Ag+ reduction and active
metal (Cu, Fe, and Zn in the Cu alloy substrates) dissolutions,
the deposition of Ag onto the substrates would occur.6 In a
previous study, Ag films composed of grains and dendrites were
formed on the same Cu alloy substrates when dipping the
substrates into AgNO3 aqueous solutions.6 In this case, different
morphologies of Ag films were formed when dipping the same
substrates into AgCl DES solutions, which might be attributed
to the different viscosities and speciations between the AgNO3
aqueous and AgCl DES solutions.

Figure 1 shows the surface morphologies of as-deposited Ag

films from 0.01 M AgCl DES solution at RT as a function of
deposition times. It can be seen that nanostructured Ag is formed
where the grain sizes are in the range of 20-40 nm with a
deposition time of 1 min. When prolonging the deposition time
to 5 min, grains are readily connected with each other as shown
in Figure 1b. Interestingly, it is found that the connected Ag
grains with a kind of self-assembly produce nanosized pores
between them, which constructs an open, bicontinuous highly
porous network with ligament and pore size in the range of
15-55 nm. The morphology of the nanoporous Ag films is very
similar to the reported nanoporous Au fabricated by the wellknown dealloying strategy.29-32 At the deposition time of 10
min (Figure 1c), the average ligament size increases from 37
nm to 40 nm and the average pore size decreases from 32
nm to 30 nm with the comparison of Figure 1b and 1c.
Moreover, some larger Ag grains with the size of 100 nm are
grown on the nanoporous Ag films. The corresponding distributions of ligament and pore sizes are given in Figure 3. Figure
1d gives the EDS mapping analysis corresponding to Figure
1c, which indicates that the film is composed of pure Ag.
It was reported that the viscosity of the DES changed
significantly as a function of temperature and that increasing
the temperature would decrease the viscosity of DES.20 Here,
we also changed the plating temperature to see the temperature
effects on the plating process. Figure 2 gives the surface
morphologies of as-deposited Ag films from 0.01 M AgCl DES
solution at 50 C as a function of deposition time. Obviously,
the deposition rate is significantly increased at the higher plating
temperature. After the deposition time of 1 min, self-assembled
nanoporous Ag films are formed on the Cu alloy substrate as
shown in Figure 2a. As summarized in Figure 3, the average
ligament size of porous Ag is 35 nm with a size range of 20-45
nm. When further increasing the deposition time to about 30
min, it is found that the average ligament size of porous Ag

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Gu et al.

Figure 2. Surface morphologies of as-deposited Ag films on Cu alloys from 0.01 M AgCl DES solution at 50 C. The deposition time is (a) 1,
(b) 5, and (c) 30 min. (d) Typical cross section SEM image of as-deposited porous Ag films. The sample shown here is obtained from 0.01 M AgCl
DES solution at 50 C for about 30 min.

Figure 3. Distributions of ligament and pore sizes in the nanoporous

Ag films as shown in Figures 1 and 2.

increased to about 75 nm as shown in Figures 2c and 3.

Furthermore, the inset of Figure 2c indicates that plenty of Ag
grains with sizes of about 10 nm were formed on the ligaments
of porous Ag. However, the pores between the ligaments of
Ag still exist with a size range of about 15-35 nm. The
nanoporous metals made by dealloying, such as Ag and Au,
generally possess three-dimensional porous structures and have
been extensively investigated because of their great potential

for applications in heterogeneous catalysis, electrocatalysis, fuel

cell technologies, biomolecular sensing, surface-enhanced Raman scattering, and plasmonics.30-33 Figure 2d gives a typical
cross section SEM image of the porous Ag films, which shows
that there are some nanoscaled pores in the films as indicated
by arrows. Clearly, the density of pores in our case is less than
the reported nanoporous metals made by dealloying.30-33 In our
case, it is the porous structures that facilitate the sustainable
deposition of Ag on Cu substrates.
Significantly, it is the first time to report the fabrication of
nanoporous Ag films by galvanic replacement reactions. Here,
we suggest that it might be the soft template effect of the viscous
DES that is responsible for the formation of nanoporous Ag.
At the beginning of the depositions, Ag grains are formed on
the substrate as shown in Figure 1a. The DES fills the
interspaces of Ag grains or pores between the Ag ligaments.
On one hand, the DES could supply Ag+ for the sustainable
deposition. On the other hand, the DES could restrict the further
growth of Ag ligaments to a certain extent thus forming the
nanoporous structures of Ag. Considering that the galvanic
replacement reaction is facile to operate compared with the
metallurgy-dealloying process, it would be more promising to
perform the catalytic and optical applications with our nanoporous Ag films.
The Ag+ concentration in the DES solution also influences
the morphology of Ag deposits. Figure 4 is the SEM images of
as-deposited Ag films on Cu alloys from 0.1 M AgCl DES
solution at RT, which is much distinguished from those obtained
from 0.01 M AgCl DES solution at RT as shown in Figure 1.
After the deposition time of 20 s, plenty of Ag grains are
randomly distributed on the substrate, which exhibits a bimodal
grain size distribution where 10-20 nm sized grains are
embedded in the 200-300 nm sized grains as shown in Figure
4a. In this case, no self-assembled porous network of Ag, the
same as the ones shown in Figures 1 and 2, is formed. Moreover,
some of the Ag grains are faceted indicating that the crystal-

Fabrication of Nanoporous Silver Film on Copper

J. Phys. Chem. C, Vol. 114, No. 32, 2010 13617

Figure 4. Surface morphologies of as-deposited Ag films on Cu alloys from 0.1 M AgCl DES solution at RT. The deposition time is (a) 20 s, (b)
1 min, and (c) 5 min.

lographic planes with low surface energy are preferentially

exposed. When increasing the deposition time to 1 min, the size
of the faceted Ag grains increases to 300-500 nm, and about
10 nm sized Ag grains also could be found at the gap of larger
grains (see Figure 4b). Furthermore, multiply twined grains with
a 5-fold symmetry also appeared at this deposition time, which
is highlighted by white lines in Figure 4b. The multiply twined
grains are thermodynamically more stable, often in the decahedral shape, and are bound almost entirely by the lower energy
{111} facets.34,35 We also find that several multiply twined grains
are coalesced together by sharing common crystallographic
orientations, which should be attributed to the oriented attachment growth mechanism.4,36 The substrate has been fully covered
by the Ag grains after the deposition time of 1 min. However,
the randomly distributed Ag grains with different sizes bring
abundant voids in the film, which could make Ag+ ions penetrate
the Ag film and react with the Cu alloy substrate thus facilitating
the sustainable deposition of Ag.27 Figure 4c gives the surface
morphology of as-deposited Ag films from 0.1 M AgCl DES
solution at RT for 5 min deposition. The major difference
between Figure 4b and 4c is that some nodular structures with
the size of about 10 nm are formed on the larger Ag grains
thus making the faceted Ag grains lose their regular geometries.
More importantly, several nanometric voids also exist around
the Ag grains even after the deposition time of 5 min. Thus,
the films obtained from 0.1 M AgCl DES solution at RT can
also be called porous Ag.
Figure 5 shows XRD patterns of as-deposited Ag films on
Cu alloys from 0.01 M AgCl DES solution at RT for 10 min
and at 50 for 30 min and 0.1 M AgCl DES solution at RT for
10 min. In Figure 5, the peaks indexed by filled squares and
filled cycles are assigned to the face-centered cubic (fcc) pure
silver and fcc Cu. The silver lattice constant calculated from
the XRD pattern is about 4.081 , a value in agreement with
the reported a ) 4.086 from JCPDS 04-0783.
Both the surface roughness and the low surface energy coating
are prerequisites for synthesizing superhydrophobicity.2,4,6 The

Figure 5. XRD patterns of as-deposited Ag films on Cu alloys from

(a) 0.01 M AgCl DES solution at RT for 10 min and (b) at 50 for 30
min and from (c) 0.1 M AgCl DES solution at RT for 10 min.

wetting properties of the Cu alloy substrate and the porous Ag

films before and after surface modification were characterized
by water CA tests, and the results are summarized in Figure 6
and Table 1. It is believed that the surface modification process
by immersing the substrate in an ethanol solution of ndodecanethiol (1 10-3 M) overnight could confer the surface
a low surface energy coating which is a self-assembled
monolayer of surface-active molecule. As shown in Figure 6,
the Cu alloy surface after modification with n-dodecanethiol
has a CA value of about 91 ( 1, which is similar to that before
surface modification. However, as for the as-deposited Ag films,
the CA values decrease with the deposition times. On the
contrary, after the surface modification process, the CA values
increase with the deposition time. It further gives the evidence
that both the surface roughness and the low surface energy
coating play dominant roles in controlling the wetting properties
of the solid surfaces. Under the same deposition time of 5 min,
the samples of porous Ag film obtained from the three plating

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J. Phys. Chem. C, Vol. 114, No. 32, 2010

Gu et al.
interface.38,39 It is therefore expected that the distinct surface
wetting for Ag films with nanosized grains observed above can
be described using the well-known Youngs equation, cos )
(SG - SL)/LG, by considering the size dependences of SG
and SL.37 In this equation, represents the surface tensions
involved in the system, is the contact angle, S is the solid, L
is the liquid, and G is the gaseous phase. However, it is not
feasible since this equation is only applicable to a liquid droplet
on a flat surface,5 while the surface is rough in our case. Instead,
the water CA on rough surfaces should be explained with the
roughness in light of the other two models, namely, Wenzel40
and Cassie-Baxter41 models. In the Wenzel model, the CA is
given by

cos w ) r cos

(1)

where r is the roughness factor defined as the ratio of the actual

area of a rough surface to the projected area, is the CA on
the corresponding smooth surface, and w is that of the rough
surface. Since r is greater than 1 because of roughness, there
are two situations for this model: for < 90, w< ; for >
90, w > .
On the other hand, assuming a water CA of 180 for air and
for a flat surface of solid, the modified Cassie-Baxter model42
derived the nominal contact angle c as

cos c ) fcos + (1 - f)cos 1800 ) f (1 + cos ) - 1

(2)

Figure 6. (a) Variation of water CA with depositon time. Solid and

open symbols denote the CA values of Ag films at as-deposited states
and at surface-modified states, respectively. The CA of Cu substrate
holds the stable value of 91 ( 1 as indicated by the shadow region.
(b) CA hysteresis of the surface-modified sample obtained from 0.1 M
AgCl DES solution at RT.

conditions studied in this paper exhibit very distinctive wettability as shown in Table 1. Significantly, after the surface
modification process, the sample obtained from 0.1 M AgCl
DES solution at RT for about 5 min exhibits a superhydrophobic
surface with a CA of 160 ( 1 as shown in Figure 6 and Table
1. The CA hysteresis () is defined as the difference between
advancing (a) and receding angles (r), which is about 30 for
this case, as shown in Figure 6b.
For nanoscaled materials, the surface or interface energy is
found to decrease as the size declines,37 which can be explained
by the atomic coordination imperfection at the surface or

where f is the area fraction of the liquid-solid contact to the

nominal contact area. Equation 2 indicates obviously that c
increases with decreasing f meaning that c increases with the
increasing fraction of air trapped in the film surface during the
contact tests.
The smooth surface of Ag was prepared by polishing bulk
Ag to a mirrorlike finish surface. The surface wettability of the
as-polished smooth Ag is studied by CA measurement, which
gives a CA value of 79 ( 1. This value is much the same as
the reported one by Safaee et al.7 The corresponding image of
a water droplet of about 1 L on the smooth silver surface is
given in Figure 7. Moreover, after the same surface modification
process as the porous Ag films, the smooth silver surface still
holds its original wetting property. In the present study, Wenzel
(eq 1) and Cassie-Baxter (eq 2) models are used to qualitatively
illustrate the importance of the surface roughness of the Ag films
at as-deposited states and at surface-modified states, respectively.
With eqs 1 and 2 and ) 79, the values of r and f are
calculated for the samples shown in Table 1. According to the

TABLE 1: Comparison of CA Values of the Ag Film Surfaces before and after the Surface Modification with n-Dodecanethiola

The Ag films were obtained from 0.01 M AgCl DES solution at RT and at 50 and from 0.1 M AgCl DES solution at RT. All samples
were obtained for the deposition time of 5 min. The corresponding r and f values are calculated from eqs 1 and 2, respectively.

Fabrication of Nanoporous Silver Film on Copper

J. Phys. Chem. C, Vol. 114, No. 32, 2010 13619

References and Notes

Figure 7. Image of a water droplet of about 1 L on the smooth silver

surface with water CA of 79 ( 1.

definition of r, it can be implied that higher r values should

correspond to the rougher surfaces. Similarly, according to the
definition of f, a smaller f value should indicate that a larger
fraction of air is trapped between the Ag films and the water
drop. Clearly, the calculated results are consistent with the
surface topographies of the films by SEM observations (Figures
1b, 2b, and 4c). It can be concluded that without the low surface
energy coating on the nanoporous Ag films, the CA value
decreases as the surface roughness increases, which should be
due to the two- or three-dimensional capillary effect of the many
nanosized pores of the films.42 With the low surface energy
coating on the nanoporous Ag films, the CA value increases
with increasing the surface roughness, which is attributed to
the many more air pockets that repel water droplets offered by
a larger surface roughness.6
4. Conclusions
Porous Ag films with fcc structures on copper alloy substrates
were fabricated by the galvanic replacement reaction from the
AgCl DES solutions. It was interestingly found that a selfassembled nanoporous network of Ag films with ligament and
channel width in the range of 20-80 nm was formed on the
Cu alloy substrate from 0.01 M AgCl DES solution either at
RT or at 50 C. However, by increasing the concentration of
AgCl to 0.1 M, Ag films constructed by randomly distributed
Ag grains and abundant voids were formed on the Cu alloy
substrates. It was suggested that the soft template effect of the
viscous DES should be responsible for the formation of
nanoporous Ag. Water CA values of the as-deposited Ag films
were decreased with increasing the surface roughness of the
films. However, after surface modification by a monolayer of
n-dodecanethiol, the CA values of porous Ag film increased
largely with the plating time. As for the sample obtained from
0.1 M AgCl DES solution for about 5 min deposition, a
superhydrophobic surface was finally obtained with a contact
angle of 160 ( 1. With the analysis by Wenzel and
Cassie-Baxter models, it was implied that the surface roughness
plays an important role on the wetting property of the Ag films.
Acknowledgment. This work was supported by the Fundamental Research Funds for the Central Universities (grant no.
2009QNA4006) and by the Research Foundation of Education
Bureau of Zhejiang Province under grant no. Y200906938.

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JP105182Y