Microscopy: Science, Technology, Applications and Education

A. Mndez-Vilas and J. Daz (Eds.)

______________________________________________

A study on the surface roughness of electrodeposited silver thin films

using a confocal laser scanning microscope
M. Saitou
Department of Mechanical Systems Engineering, University of the Ryukyus, 1 Senbaru Nishihara-cho Okinawa,
903-0213, Japan
We have investigated the surface roughness of silver thin films electrodeposited by a direct or pulse current technique
using a confocal laser scanning microscope. Our reasech is twofold: (1) In direct current deposition, antimony potassium
tartrate as an additive shows a large effect on the surface appearances of the silver thin film electrodeposited from a silver
ferrocyanide-thiocyanate electrolyte. Phase diagrams of the appearance stability indicate that the silver ferrocyanidethiocyanate electrolyte including antimony potassium tartrate allows the silver thin film with the shiny appearance within a
narrow region of cathode potential. The surface roughness of the silver thin film measured with the confocal laser scanning
microscope reveals that the shiny appearance corresponds to the two-dimensional growth that results in the smooth surface
and the black appearance does to the three-dimensional growth characterized by vertical growth. Cyclic voltammetry
curves exhibit that the shiny appearances are related to a rapid increase in the current density within the narrow region of
the cathode potential. (2) In pulse current deposition, the effect of three parameters such as the pulse current amplitude,
current on-time, and current off-time on the surface roughness of the silver thin film deposited from the electrolyte free of
antimony potassium tartrate has been investigated using the confocal laser scanning microscope. An interface width
defined by the root mean square of fluctuations in surface height is found to decrease with the current off-time and to
increase with the current on-time. Only in the case of the sufficient current off-time, the interface width decreases with the
pulse current amplitude. These experimental results indicate that the appropriate choice of the current on-time and off-time
enables the fabrication of the silver electrodeposit with a small surface roughness.
Keywords confocal laser scanning microscope; surface roughness; silver; electrodeposition, shiny appearance

1. Introduction
A silver thin film with a smooth and shiny surface is of importance for decorative, industrial and technological
application [1, 2]. A cyanide electrolyte including a leveling agent has been employed in silver electrodeposition
because the silver cyanide concentration can be easily controlled in a cyanide process. Environmental regulations for
wastewater discharges polluted by cyanide, and cyanide hazards during the process have urged the research and
development of cyanide-free processes in silver electrodeposition. The leveling agent such as antimony potassium
tartrate (APT) [3-5] is also a toxic compound. Hence, low toxic silver electrolytes are required for the environmental
regulations and cyanide hazards.
Terminology such as a shiny, white bright, and black apperance has been conventionally used because of a visual
check that is a simple method to represent the surface appearances of electrodeposits. Unfortunately, using electrolytes
containing cyanide-free silver compounds [3-6] such as silver nitrate, silver sulfate, silver ionide and silver thiosulfate
the silver thin film with the shiny appearance has not been produced.
Leveling and brightening additives in electrodeposition adsorb preferentially at active sites in a surface and suppress
growth perpendicular to a substrate. APT in silver electrodeposition is known to be a brightening agent [7] and reported
to make it possible to form patterns in the silver thin film [8-9]. However, there have been very few studies on the
effect of APT on the surface appearance of the silver thin film.
Pulse electrodeposition is applied to produce a deposit with a finer grain size in comparison with direct current (DC)
electrodeposition. The influence of three pulse-parameters such as an amplitude of pulse current, current on-time, and
current off-time on the electrodeposit has been investigated [10-18]. According to the overall conclusion of the studies,
it is difficult to predict a priori the influence of these parameters because each electrochemical system reacts in a
different way. In fact, the grain size in Zn electrodeposition [18] decreases with the current on-time whereas the grain
size in Ni electrodeposition [14] increases with the current on-time. Surface roughness is usually related to the grain
size of electrodeposited thin films.
In this study, a silver ferrocyanide-thiocyanate electrolyte synthesized by a method referred in [8-9,19-20] is
employed as a low toxic one. Using the silver ferrocyanide-thiocyanate electrolyte including APT, phase diagrams are
made so as to find a cell voltage and current density, which yield the silver thin film with the shiny appearance. An
interface width [21] that characterizes the surface roughness, which is observed with a confocal laser scanning
microscope, is introduced to relate the shiny, white bright, and black surface appearance.
The purposes of the present paper are to show that using the confocal laser scanning microscope, the shiny
appearance of the silver thin film deposited from the silver ferrocyanide-thiocyanate electrolyte including APT is

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related to the two-dimensional growth, and that the appropriate choise of the three parameters in pulse current
electrodeposition allows the silver thin film with a small roughness.

2. Experimental setup
Experiments were performed using the two kinds of electrolyte that includes the following components (gL-1): (1) in
DC electrodeposition, AgNO3, 25.5; K4Fe(CN)63H2O, 72; KSCN, 146; KNaC4H4O64H2O, 59.3; C8H4K2O12Sb23H2O
(APT), 5, 10 and 15; K2CO3, 31.3; (2) in pulse current electrodeposition, AgNO3, 25.5; K4Fe(CN)63H2O, 72; KSCN,
146; KNaC4H4O64H2O, 59.3; K2CO3, 31.3. The mixed solution of AgNO3, K2CO3 and K4Fe(CN)63H2O, which
solution was boiled for 30 minutes, yielded burnt umber precipitates of iron hydroxides. After removal of the iron
hydroxide, the remaining components were added into the solution. Thus, the electrolyte [22] containing APT or that
free of APT was synthesized. The two electrolytes having the pH of about 8.2 were low toxic ones comprising the
complex agent [19-20] Ag(CN)2CNS-(+1) where has a value between 1 and 2.
In this study, the salt KNaC4H4O6 was employed as a stabilizer. The concentration of Ag+ in the electrolyte was very
low because most of the silver ions were incorporated into the complex agent Ag(CN)2CNS-(+1) and very few neutral
complexes were formed by Ag+ and tartaric monoanions [22-25]. Hence, potassium sodium tartrate in the electrolyte
had little influence on surface roughness. In fact, in our preliminary experiment using the solution with or without
potassium sodium tartrate, there was no difference in the surface roughness of silver thin films.
A poly-crystalline copper and carbon plate of 30x10 mm2 each were prepared for a working and counter electrode.
The copper substrate of 99.9 wt% purity had a mirror-like appearance. The two electrodes cleaned by a wet process
were located parallel in a quiescent electrochemical cell at a temperature of 300 K. A fixed voltage or current was
applied with an electric power supply across the electrochemical cell and a resistor. The resistor having the resistance of
50 to 100 , was connected in series with the electrochemical cell to change the cell voltage and current. In DC
electrodeposition, the current through the electrochemical cell and the cell voltage between the cathode and anode
electrode were calculated from the potential drop across the resistor. The cathode potential was measured with a Luggin
capillary with a Ag/AgCl electrode in a KCl solution. On the other hand, in pulse current electrodeposition, a square
wave pulse current having a peak current density Jp of 2 to 24 mAcm-2, current on-time Ton of 1 to 100 msec, and
current off-time Toff of 1 to 900 msec was applied with the power supply. The cathode potential was measured with the
Luggin capillary and was recorded into a digital storage oscilloscope.
The surface morphology of the silver thin film was observed with the confocal laser scanning microscope (Keyence
VF7500) to an accuracy to 0.01 m in height. The interface width [21] was calculated from the surface profile of the
surface comprising 512 pixels measured with the confocal laser scanning microscope. The interface width that means
the standard deviation of the surface roughness is defined by
1/ 2

1 N
2
w(t ) = (hi h )
N

i =1

(1)

where t is the growth time, N is the number of pixel, hi is the surface height and
length of the surface profile.

h is the average height over the lateral

3. Results and Discussion

The charge transfer reaction of the Ag complex agent in silver electrodeposition [26] becomes
Ag (CN )2 CNS ( +1) + e Ag + 2CN + CNS .

(2)

The cell voltage and current through the electrochemical cell were changed by the resistor connected in series with
the electrochemical cell.
3.1

Silver thin film in DC electrodeposition

3.1.1 Phase diagram of surface appearance

Figure 1 shows the phase diagram of the appearance stability for the silver thin film electrodeposited from the
electrolyte including APT of 5 to 10 gL-1. Terminology such as the shiny, white bright, and black appearance is used to
represent the surface appearance in a conventional fashion. The white bright appearance means the bright but slightly
smoked surface appearance. The shiny appearance is produced within a narrow cell voltage ranging from 1.2 to 1.35 V.
An increse in the concentration of APT makes the region of shiny appearance shifted to a larger current and cell
voltage.

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In order to relate the surface appearance to the interface width defined by Eq. (1), the surface height hi is measured
with the confocal laser scanning microscope to an accuracy to 0.01 m in height. The copper substrate that appears to
be mirror-like have an average interface width of 0.05m. Figure 2 shows the optical microscope images of the silver
electrodeposits and surface profile. The average growth rate was 0.35m min-1 at a current density of 7.5 mAcm-2 and
the typical film thickness in Fig.2 was about 1.6 m. The interface width of the silver thin film with the shiny
appearance has a smaller value of 0.03 m than that of the copper substrate. The interface width of the silver thin film
with the white bright appearance has the same value as that of the copper substrates. This indicates that the lateral
growth of the shiny silver thin film makes it possible to have the smaller interface width. On the other hand, the
interface width with the black appearance has a much larger interface width of 0.64 m. Thus, the interface width is
shown to correspond to the surface appearance determined by the view check. In addition, the two dimensional and
three dimensional growth mode can be related to the shiny appearance and black appearance.

Fig. 1 Phase diagrams of appearance stability for the silver electrodeposits determined with the view check. The symbol, shiny means
the mirror-like and bright appearance. White bright means the bright but slightly smoked or blunt appearance. Black means the color
of black. The concentration of APT in the solution is (a) 5 gL-1 and (b) 10 gL-1.

Fig. 2 Typical microscope images and surface profiles measured with the confocal laser scanning microscope. The electrodeposits
have a film thickness of about 1.6 m. The average interface width defined by Eq.(1) is (a) 0.05 m for the white bright appearance,
(b) 0.03 m for the shiny appearance. The copper substrates have an average interface width of 0.05 m.

3.1.2 Current-potential curve

The cathode potential measured with the Luggin capillary immersed into the electrolyte in the vicinity of the copper
electrode is shown in Fig.3. It is evident that APT causes a rapid rise of the current density in a region of the symbol A
in Fig.3. The cathode potential in a region of A is almost within a narrow range from 0.55 to 0.65V, which value is
independent of the sweep rate. At the rapid current rise the shiny appearance deposits are produced whereas it is
believed that the rapid increase in the current forms the rough surface owing to the dendrite growth. However, by
repeating the experiments many times we ascertain that the cathode potential in the region of A for the shiny appearance
deposits are obtained
Next, we investigate whether or not the cathode potential ranging from 0.55 to 0.65 V corresponds to the cell voltage
ranging from 1.2 to 1.35 V in Fig. 1, at which the siver thin film with the shiny appearances yields. When the cell
voltage and current density were 1.3 V and 5.5 mAcm-2 in the electrolyte containing APT of 15 gL-1, the cathode
potential of 0.6V were measured using the Luggin capillary and the silver thin film with the shiny appearance was

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formed. It is concluded that at the cell voltage ranging from 1.2 V to 1.35 V, the cathode potential takes a value ranging
from 0.55 to 0.65V. Thus, the film growth with the shiny appearance occurs in the region A.

Fig.4 A log-log plot of the interface width w(t) vs. the growth time
t for the deposits with the black appearance at a current density of
5.6 mAcm-2, a cell voltage of 1.62 V and APT of 15 gL-1.

Fig.3 Typical cyclic voltammetry curves for the

electrolyte free of antimony potassium tartrate
and for that including APT of 15 gL-1 .

These experimental results suggest that the effect of APT on electrodeposition is different from that of other leveling
additives that suppress the growth of electrodeposits owing to their adsorption at active sites in the surfaces. The
leveling additives do not generally cause an increase in the current density. However, APT in the region A at which the
silver thin film with the shiny appearance grows shows the rapid increase in the current density.
Here, according to a simple perturbation theory, we make an attempt for explaining the effect of the rapid rise of the
current density on electrodeposition. A height fluctuation that takes place in the smooth surface is set as hsint where
h is the amplitude of the height fluctuation, is the angular frequency, and t is the time. The height fluctuation formed
under a current i and cathode potential may develop or decay with time. The fluctuation of the growth rate v caused
by the height fluctuation is given by
d
(3)
v = h sin t.
dt
As a change in the current density i is proportional to v, we have

i=

zF
h cos t ,
M

(4)

where M is the molecular weight, z is the valence number, is the density and F is the Faradays constant. On the other
hand, a Butler-Volmer equation for the cathode potential has the form:
zF
(5)
i = io exp
,
RT
where io is the exchange current density, is the charge transfer coefficient for the cathode reaction, R is the gas
constant, and T is the temperature. If a change in the cathode potential caused by the fluctuation is small, for ||<1,
Using the result of Eq. (5), Eq.(4) yields
(6)
h i .
Eq. (6) means that the height fluctuation will remain small if the current density i and the cathode potential
fluctuation in the system are small. This conclusion is just true for the silver thin film with the shiny appearance. The
fluctuation of the potential in the A region in Fig.3 is estimated at less than 0.1V. The current density is also small in
comparison with the current density in the region B where the deposits with the black appearances grow. Consequently,
as the height fluctuation remains small, the surface apperance remains shiny.

3.1.3 Scaling behavior of the tnterface width

Figure 4 shows the interface width of the silver thin film with the black appearance. The interface width is initially
independent of time, however, at more than 100 s increases with time. The surface appearance at less than 100 s appears
to be shiny. The interface width is known to obey the equation [21]:
(7)
w(t ) t ,
where is called the growth exponent. The value of in Fig.4 is 5.5, much larger than 0.5, which indicates that
anomalous growth takes place locally [28-29].

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3.2 Silver thin film deposited from the electrolyte free of additives by a pulse current technique
Figure 5 shows a typical surface image of a silver thin film of 1 m in thchness and surface profile measured with the
confocal laser scanning microscope. The silver thin film was electrodeposited from the electrolyte free of APT. The
surface appearance is white bright and the interface width becomes 0.08m. The silver thin film of 1m in thickness is
thick enough to use for printed circuit boards and decorative applications.

Fig.5 Microscope image of the silver thin film grown at Jp=12 mAcm-2 , Ton = 9 ms, and Toff=14 ms.The surface profile was
measured with the confocal laser scanning microscope.

3.2.1 Effect of the pulse current amplitude Jp

A plot of the interface width vs. the cathode potential measured at a current on-time of 1 msec and current off-time of 9
msec is shown in Fig. 6(a). The interface width decreases with the pulse current amplitude Jp whereas the cathode
potential increases with Jp. The experimental result seems to be consistent with the studies on nickel [17] and zinc
electrodeposits [18], which explain that the relationship between the fine grain size and high pulse current density is due
to the nucleus radius of the deposit inversely proportional to the cathode potential. The higher current density yields
finer grain sizes because the higher electrode potential increases the free energy available for the formation of new
nuclei and results in a higher nucleation rate. A finer grain of the deposits becomes a smaller interface width w(t) [18].

Fig.6 A plot of the interface width and cathode potential for a variation of the pulse current density. (a) Ton =1 ms and Toff = 9 ms, (b)
Ton =100 ms and Toff = 900 ms.

To confirm the effect of Jp, w(t) was measured for the deposits grown at a much larger current on-time of 100 msec
than 1 msec. Fig. 6(b) shows that the interface width decreases with Jp as well as Fig. 6(a). The film thickness and the
ratio Ton/Toff are the same as those in Fig.6 (a). Irrespective of Jp, w(t) in Fig. 6(b) is larger than that in Fig. 6(a). This is
because of the longer current on-time at which the grain growth occurs.

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However, Figs. 7 (a) and (b) show that an increase in Jp does not always decrease the interface width. The current
on-time and off-time in Fig.7 (a) are 4 msec and 6 msec, and those in Fig.7 (b) 9 msec and 1 msec. As expected, an
increase in Jp causes an increase in the cathode potential. According to Figs.7 (a) and (b), it is not simply said that an
increase in the cathode potential decreases the interface width.

Fig.7 A plot of the interface width vs. the cathode potential for a variation of the pulse current density. (a) Ton=4 ms and Toff = 6 ms.
(b) Ton =9 ms and Toff = 1ms.

3.2.2 Effect of the current off-time Toff

Figure 8 shows a plot of the interface width w(t) and the cathode potential for a variation of the current off-time. The
silver thin film was grown at a current on-time of 9 msec. An increase in Toff rapidly decreases the interface width,
which tends to saturate at the current off-time of 12 msec. The presence of some adsorbed compound formed through
electrochemical reactions [8-9, 14] is believed to act as a leveling agent during the current off-time even if no leveling
agent is added in the solution. At the current off-time above 12 msec, the interface width reaches a stable value. Figure
8 indicates that it takes at least 12 msec for the adsorbed compound to cover all of the active sites in the cathode. Hence,
there exists a limitation period beyond which the current off-time has no influence of a decrease in the interface width.
In this study, cyanide [30] or thiocyanate ions may become an adsorption compound during the current off-time. The
active site means a site available for nucleation. Hence, the adsorbed ion suppresses nucleation or growth at the active
site and the deposit results in the smooth surface. Anyway, it is shown that in silver electrodeposition the current offtime has a significant influence on the interface width and the limitation period of the current off-time at which the
effect of the current off time is lost exists.

Fig.8 Dependence of the interface width and cathode

potential on the current off-time at a fixed current on-time
of 9 ms and at a pulse current density of 12 mAcm-2.

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Fig.9 Dependence of the interface width and cathode

potential on the current on-time at a fixed current off-time
of 9 ms and at a pulse current density of 12 mAcm-2.

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3.2.3 Effect of the current on-time Ton

Figure 9 shows a plot of the interface width w(t) and cathode potential for a variation of the current on-time. The
interface width initially decreases somewhat and rapidly increases with the current on-time. In Zn electrodeposition
[16], the grain size decreases with the current on-time (hence the interface width also decreases) because an increase in
the current on-time causes a decrease in the cathode potential.
However, in Fig.9, the cathode potential increases with the current on-time. An increase in the cathode potential
seems to cause an increase in the interface width. The current off-time may be so short that the formed compound can
not adsorb at all active sites. In fact, as seen in Fig. 6(b), if the current off-time is long enough for the compound to
adsorb, for instance, at a current on-time of 100 msec, the interface width will decrease.
3.2.4 Duty ratio and interface width
The duty ratio defined by Ton/(Ton+Toff)=1/(1+Toff/Ton) makes the influence of the current on-time and off-time evident.
As seen in Figs. 6 and 7, the interface width holds small for Toff /Ton>>1 and increases for Toff /Ton<1.5.
Figure 10 shows the dependence of the interface width on the duty ratio. The interface width initially holds 0.10.04
m within fluctuations. An abrupt change of the interface width is observed at a ratio of about 50 % in Fig.10. This
rapid increase corresponds to Ton=Toff.
In summary, Ton<10 msec and Toff>12 msec are necessary for a silver deposit with a smaller surface roughness. In
fact, as shown in Fig. 6, the silver electrodeposit with the smooth surface is obtained by the appropriate choice of the
current on-time and off-time.

Fig. 10 A plot of the interface width vs. the duty ratio at a pulse current density of 12 mAcm-2. Here, the duty ratio is defined by
Ton/(Ton+Toff).

4. Conclusions
The effect of APT on the surface appearances of the silver thin films from the silver ferrocyanide-thiocyanate
electrolyte has been investigated to produce the silver deposits with the shiny appearances. The phase diagrams exhibit
the presence of the shiny appearance within a small range of the cathode potential. The interface width of the
electrodeposits measured with the confocal laser scanning microscope reveals that the shiny and black appearances
correspond to two-dimensional growth and three-dimensional growth. The cyclic voltammetry curves show that the
shiny appearances can be related to the presence of the rapid increase in the current density. Hence, the effect of APT
on the surface roughness is different from that of other leveling additives that suppress vertical growth of
electrodeposits owing to their adsorption at the active sites on the surfaces.
The effect of the three parameters, Jp, Toff, and Ton on the surface roughness of the silver thin films has been
investigated using the confocal laser scanning microscope. The experimental results show that (1) the interface width
rapidly decreases at the longer current off-time than the current on-time, (2) the long current on-time increases the
interface width, and that (3) for the sufficient current-off time in comparison with the current on-time, the interface
width decreases with the pulse current density. In this study, the adequate choice of the current on-time and off-time
allows the silver electrodeposit with the small surface roughness.

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