Electrocrystalization
G Staikov, Institute of Solid State Research (IFF-b), Research Center Jülich, Jülich, Germany
& 2009 Elsevier B.V. All rights reserved.
Introduction
Electrocrystallization refers to nucleation and crystal
growth occurring on electrodes in electrochemical sys-
tems under the influence of an electric field. Nucleation
and growth phenomena are involved in many battery
systems, where the electron transfer is coupled to various
phase transformations occurring during charge and/or
discharge in the active electrode materials. For example, in
the lead–acid battery the electrochemical reactions in-
volve formation of different electronically conducting and
insulating crystal phases (e.g., lead, lead dioxide (PbO2),
lead sulphate (PbSO4), which have a decisive influence on
the characteristics and operational life of the battery.
Electrocrystallization is also a basis for technologically
important electrochemical processes such as electro-
deposition, passivation, and electrorefining. The electro-
deposition has recently become of particular importance
for the development of modern micro- and nanosystem
technologies. A typical example is the developed elec-
troplating technology for fabrication of submicron copper
on-chip interconnects of microelectronic devices. Elec-
trocrystallization processes are not only of technological
interest but, in many cases, also offer excellent possibilities
for investigating the fundamental aspects of nucleation
and crystal growth. This is mainly because in electro-
chemical systems the driving force and the rate of crys-
tallization can be measured and controlled with high
accuracy by the electrode potential and the current.
Typical electrochemical reactions involving phase for-
mation and crystal growth phenomena are: (i) cathodic
electrodeposition of metals, semiconductors, and alloys;
(ii) anodic electrodeposition of semiconductors; and (iii)
anodic formation of insulating layers (passive layers) on
metallic and semiconducting substrates.
The overall electrocrystallization processes are com-
plex; in addition, the phase formation phenomena involve
ion transport in the electrolyte and charge transfer across
the electrode/electrolyte interface. Additional compli-
cations can arise due to chemical reaction steps and/or
parallel electrochemical reactions. The simplest con-
ditions can be realized in the case of electrodeposition of
a metal (Me) from an electrolyte containing simple metal
ions (Mez þ ):
Mezþ þ ze -Me ½I
Two situations can be generally considered: (1) formation
of the new Me phase on an inert foreign substrate and
32
(2) electrodeposition on a substrate of the same metal
Me, which corresponds to the growth of the three-di-
mensional (3D) Me crystal phase. The case of electro-
deposition on foreign substrate (1) is more general
because the advanced deposition stages of the process
always involve the crystal growth of the 3D Me phase.
The mechanism of initial stages of Me deposition on
foreign substrates depends strongly on the Me–substrate
interaction and the crystallographic misfit between the
bulk 3D Me crystal phase and the substrate. At a rela-
tively weak Me–substrate interaction, the deposition
process starts at electrode potentials E more negative
than the Nernst equilibrium potential of the 3D Me
phase (EoE3DMe) with the formation of isolated 3D
Me crystallites on an unmodified foreign substrate
(Figure 1(a)). This deposition mechanism is not affected
by the Me–substrate misfit and is called ‘Volmer–Weber’
growth mode. In the case of strong Me–substrate inter-
action, however, the deposition can start even at elec-
trode potentials more positive than the Nernst
equilibrium potential (E > E3DMe) with the formation of
Me monolayers (2D Me phases), a phenomenon known
as underpotential deposition (UPD). The 2D Me phases
formed in the UPD range act as precursors for the
3D Me
(a)
2D Me
(b)
(c)
Figure 1 Schematic representation of different mechanisms of
initial deposition stages on foreign substrates: (a) Volmer–Weber
growth mode, (b) Stranski–Krastanov growth mechanism, and (c)
Frank–van der Merwe growth mode. 3D Me, three-dimensional
metal; 2D, two-dimensional metal.
 Electrochemical Theory | Electrocrystalization
subsequent formation of the 3D Me phase at EoE3DMe
and can lead to two different deposition mechanisms
depending on the crystallographic Me–substrate misfit.
In systems with significant Me–substrate misfit, the de-
position follows the so-called Stranski–Krastanov growth
mode including the formation of unstrained 3D Me
crystallites on top of a predeposited and strained 2D Me
phase (Figure 1(b)). In the rare cases of negligibly small
Me–substrate misfit, the UPD monolayers are unstrained
and the deposition of Me can take place by a layer-
by-layer mechanism known as ‘Frank–van der Merwe’
growth mode (Figure 1(c)).
The above considerations show that electrodeposition
of metals includes many 2D and 3D phase formation
phenomena, which play an important role in determining
the deposition kinetics and the evolution of morphology
and structure of metal deposits. Detailed investigations
of metal electrodeposition in various systems have
contributed significantly to a deeper understanding
of nucleation and growth and to the development of
theoretical models of electrocrystallization at an atomic
level. Therefore, in the following two sections of this
article the basic theoretical and experimental aspects of
electrocrystallization will be reviewed and illustrated
considering the kinetics and mechanism of nucleation
and crystal growth processes in the case of metal elec-
trodeposition. An approach for studies of electro-
crystallization processes relevant to the lead–acid battery
system will be discussed in a separate section.
Formation of New 3D Crystal Phase
The driving force of electrochemical formation of a new
3D Me crystal phase, the supersaturation Dm̃, is given by
the relation Dm̃ ¼ zeZ, where e is the elementary
charge and Z ¼ E  E3DMe o0 represents the cathodic
overpotential. The formation of the new phase requires
the generation of clusters with a size ensuring their
spontaneous growth at the applied overpotential Z. The
energy of formation DG̃ðnÞ of a cluster consisting of n Me
atoms can be generally expressed by the equation:
DG̃ðnÞ ¼ nze jZj þ FðnÞ ½1
where the term F(n) represents the energy excess asso-
ciated with the creation of new interfaces. At constant Z,
the function DG̃ðnÞ displays a maximum at a critical
cluster size nc, at which the cluster can grow spon-
taneously. This critical cluster is called the nucleus of the
new phase and determines the energy barrier for nu-
cleation DG̃ðnc Þ.
According to the classical nucleation model, the en-
ergy barrier DG̃ðnc Þ for the formation of 3D nuclei on a
foreign substrate can be related to nc and Z by the
33
following expression:
2 3 
4Bvm sF nc
DG̃ðnc Þ ¼ ¼ ze jZj ½2
27ðze jZjÞ2 2
where B is a geometrical factor depending on the shape of
the 3D nucleus (B ¼ 36p for a sphere and B ¼ 63 for a
cube), vm the volume of an atom in the nucleus, s the
average specific surface energy of the nucleus, and F* a
factor, which accounts for the nucleus–substrate inter-
action. The corresponding stationary nucleation rate J
can be expressed as follows:
J ¼ K1 exp½DG̃ðnc Þ=kB T  ¼ K1 expðK2 =Z2 Þ ½3
where K2 ¼ 4Bvm s F =27ðzeÞ2 kB TT . The preexpo-
2 3 
nential factor K1 depends only slightly on Z and, for small
|Z| values, can be considered as a constant. For small
nuclei consisting only of several atoms, macroscopic
quantities such as surface energy and adhesion energy
lose their physical meaning, and eqns [2] and [3] no
longer hold good. In this case, the nucleation process can
be described by the so-called atomistic nucleation model.
According to this model, the excess energy term F(n) in
eqn [1] can be expressed by
X
n
FðnÞ ¼ nfk  fi ½4
i¼1
where fk is the binding energy of an atom in the so-
called kink site or ‘half-crystal’ position of the infinitely
large bulk crystal and fi represents the binding energy of
an atom in position i of the small cluster formed on the
foreign substrate. The calculations show that in contrast
to the classical nucleation model, nc remains constant in
relatively large overpotential intervals, in which the sta-
tionary nucleation rate is described by the equation
0
J ¼ K1 exp½Fðnc Þ=kB T exp½ðnc þ 1  aÞze jZj=kB T  ½5
0
where the constant K1 includes the number density of
nucleation sites N0 and (1  a) is the cathodic charge
transfer coefficient for the transfer of metal ions from the
electrolyte to the nc-size critical nucleus under the action
of Z.
A specific feature of the J|Z| relationship is the
existence of a critical overpotential |Zcrit|. As illustrated
schematically in Figure 2, the nucleation rate J is
practically zero at jZj{jZcrit j and rises exponentially at
jZjcjZcrit j. Based on this specific behavior, a very
powerful double-pulse potentiostatic technique for
experimental investigation of nucleation kinetics was
developed. In this technique, nuclei of the new phase are
generated applying a short nucleation pulse with suf-
ficiently high amplitude jZ1 jcjZcrit j. During a following
second growth pulse with much lower amplitude
34 Electrochemical Theory | Electrocrystalization

jZ2 j{jZcrit j, the nuclei generated by the first pulse grow
to larger crystallites, which can be microscopically ob-
served. This allows the determination of the number
density of nuclei N by counting the number of crystallites
on a given substrate area. Experimental N  t depen-
dences at different overpotentials can be easily obtained
by varying the duration of the first nucleation pulse.
Figure 3 presents the illustrative experimental data
obtained by the double-pulse technique described above for
electrochemical nucleation of silver on a glassy carbon
substrate. Experimental plots of the number density of nu-
clei N versus time t (nucleation pulse duration) at different
overpotentials Z (nucleation pulse amplitudes) are shown in
Figures 3(a) and 3(b). The data for the stationary nucle-
ation rate (J ¼ dN/dt) determined from the slopes of the
linear N  t dependences are presented in Figure 3(c) in a
Nucleation rate J
ln J versus |Z| plot. The experimental ln J  |Z| de-
pendence shows two distinct linear regions in agreement
with eqn [5] and the predictions of the atomistic nucleation
model. From the slopes of the two straight lines, values
of nc ¼ 4 and nc ¼ 1 can be obtained for the number
of silver atoms in critical nucleus in the overpotential
intervals 25 mV{|Z|{51 mV and 51 mV{|Z|{90 mV,
respectively.
The overall rate of formation of the new 3D Me
crystal phase on a foreign substrate is determined by both
the nucleation rate and the growth rate of newly formed
crystallites. Two limiting cases of nucleation are usually
considered. The so-called ‘instantaneous nucleation’ re-
fers to the case when all nucleation sites N0 are converted
to nuclei virtually instantaneously at t ¼ 0, while in the
case of so-called progressive nucleation, the nucleation
sites are converted to nuclei progressively during the
whole period of observation.
In the very initial stage of phase formation, the indi-
vidual small crystallites grow independently and the
fraction of the substrate surface covered by them or their
diffusion zones is negligibly small. Under these con-

ditions, the current–time relationships can be expressed

by a general time law i(t)Bt p, where the power p depends
on the rate-determining step of metal deposition reaction
(charge transfer, ion transport) and on the nucleation
crit
type (instantaneous or progressive). For example, in the
case of crystallite growth controlled by hemispherical
diffusion, the initial current density i(t) is expressed by
Overpotential 

Figure 2 A schematic representation of the dependence of

nucleation rate J on the overpotential |Z|. jiðt Þj ¼ N0 Kd ðZÞt 1=2 ½6

50 mV
45 mV
80 40 mV
N (cm2)

60 35 mV 13

40 30 mV
25 mV
20 11

0
0 40 80 120 160 200 240
In J

9
(a) t (ms)
90 mV
80 80 mV 70 mV
60 mV 7
55 mV
N (cm2)

60

40 5
20

0 3
0 2 4 6 8 10 40 60 80 100
(b) t (ms) (c)  (mV)

Figure 3 Kinetics of electrochemical nucleation of silver on a glassy carbon electrode: (a) and (b) dependences of number of nuclei N
on time t for various overpotentials |Z|, and (c) dependence of the stationary nucleation rate J on the overpotential |Z|. Adapted from
Milchev A and Vassileva E (1980) Electrolytic nucleation of silver on a glassy carbon electrode. Part II. Steady state nucleation rate.
Journal of Electroanalytical Chemistry 107: 337–352.
 Electrochemical Theory | Electrocrystalization
for the case of instantaneous nucleation and by
2J ðZÞKd ðZÞ 3=2
jiðt Þj ¼ t ½7
3
for the case of progressive nucleation. In these equations
the growth constant Kd ðZÞ is given by Kd ðZÞ ¼
pzevm1=2
ð2DcÞ3=2 ½1  expðzeZ=kB T Þ3=2 , where D and c are
the diffusion coefficient and the concentration c of metal
ions in the electrolyte, respectively. As can be seen
from eqn [7], in the case of progressive nucleation the
nucleation rate J can be estimated from the slopes of the
|i| versus t3/2 plots of initial parts of experimental current
transients. This technique has been successfully used
for investigation of nucleation kinetics in many electro-
chemical systems with fast charge-transfer reactions
and low concentrations c.
As mentioned earlier, eqns [6] and [7] are applicable
only in the very initial stages of the phase formation
process. In the advanced deposition stages, however, it is
also necessary to take into account the reduction in the
substrate surface area available for nucleation due to the
spreading and overlap of growing crystallites and their
diffusion zones. In the existing theoretical models, the
actual fractional surface coverage y(t) is usually described
by the Kolmogorov–Avrami relation:
yðt Þ ¼ 1  exp½yext ðt Þ ½8
where yext(t) is the so-called extended fractional coverage
representing the total surface area that would be covered by
all growing crystallites disregarding their interference and
overlap. Different theoretical expressions for the overall
current transients have been derived on the basis of eqn [8]
using various approximations for the shape of growing
crystallites and their diffusion zones. A good fitting has been
obtained in many cases between experimental and theore-
tical transients. Nevertheless, it is often recommended that
the used theoretical models and the fitting parameters be
checked, whenever possible, using independent measure-
ments including direct microscopic observations.
In the advanced growth stages the surface of the
crystal consists usually of low-index faces called singular
faces, which determine the crystal growth rate. The most
important theoretical and experimental aspects of elec-
trochemical growth of singular crystal faces are reviewed
in the following section.
Growth of Singular Crystal Faces
Generally, the current density for the electrochemical
growth of a singular crystal face is determined by the
frequency of generation of monolayers fmon and can be
expressed by the equation
ji j ¼ fmon qmon ½9
35
where qmon is the charge density needed for the de-
position of one monolayer.
Optimal experimental conditions for investigation of
different growth mechanisms have been realized in the
case of electrochemical growth of isolated Ag(100) and
Ag(111) single-crystal faces prepared by the so-called
capillary technique. In this technique, a properly oriented
silver single crystal is grown in a glass capillary by
electrodeposition from an aqueous 6M silver nitrate
electrolyte solution. Applying appropriate deposition
conditions, isolated ‘quasi-perfect’ Ag(100) and Ag(111)
single-crystal faces can be produced completely free of
screw dislocations or with a limited number of screw
dislocations. Next, the various crystal growth mech-
anisms are discussed on the basis of selected experi-
mental results obtained on such ‘quasi-perfect’ silver
crystal faces in the system Ag(hkl )/6M silver nitrate.
The generation of new monatomic layers on a screw
dislocation-free singular crystal face takes place by 2D
nucleation. The kinetics and the mechanism of the
growth process are determined by the mean nucleation
time t̄n and the propagation time tp defined by the
equations
t̄n ¼ ðJAÞ1 ½10
tp ¼ Vp1 A1=2 ½11
where J is the stationary nucleation rate, A the area of the
crystal face, and Vp the rate of propagation of 2D islands
(the propagation rate of monatomic steps). Two different
growth mechanisms can be generally distinguished de-
pending on the characteristic times t̄n and tp: (1)
mononuclear layer-by-layer growth and (2) multinuclear
multilayer growth.
The mononuclear layer-by-layer growth mechanism
operates at relatively low |Z| where the mean nucleation
time is much larger than the propagation time t̄n ctp .
Under these conditions the formation of each new
monolayer involves only one 2D nucleus, which has
enough time to propagate over the whole surface before
the next nucleus is formed. The growth process is
characterized by current fluctuations connected with the
nucleation and spreading of each monolayer. The cor-
responding mean current density depends only on the
nucleation frequency (JA) and is given by
Z̄tn
1
jī j ¼ jiðt Þjdt ¼ qmon JA ½12
t̄n
0
Figure 4 shows a typical current response obtained
during the electrochemical growth of a ‘quasi-perfect’
screw dislocation-free Ag(100) crystal face at a constant
overpotential Z ¼ 6 mV. Single-current spikes (tran-
sients) that are sporadic in time are observed under these
36 Electrochemical Theory | Electrocrystalization
80
60
I (nA)
40
20
0 0
0 10 20 30 40
t (s)
Figure 4 Current transients during the mononuclear layer-by-
layer growth of a quasi-perfect (screw dislocation–free) Ag(100)
single crystal face at an overpotential Z ¼  6 mV. Electrode area
A ¼ 3  104 cm2. The insets indicate the locations of growing 2D
islands. Adapted from Budevski E, Obretenov W, Bostanov V,
et al. (1989) Noise analysis in metal deposition – Expectations
and limits. Electrochimica Acta 34: 1023–1029.
conditions. Each current transient is characterized by a
charge density equivalent to that for the formation of one
monolayer (qmon), which demonstrates clearly that the
mononuclear layer-by-layer growth mechanism operates
in this case. The shape and the duration of each current
transient depend on the location of growing 2D islands
on the crystal face as illustrated in Figure 4 (insets).
Before the interference of a growing 2D island with the
face boundaries, the growth current I1(t) increases lin-
early with time according to the equation:
jI1 ðt Þj ¼ 2qmon bVp2 t
where b is a factor that depends on the geometric shape
of the growing 2D island (b ¼ p for a disk). The propa-
gation rate Vp can be evaluated from the slope of initial
linear parts of current transients using eqn [13]. A de-
tailed statistical analysis of current–time records with
sufficiently large number of nucleation events showed
that under these conditions the process of 2D nucleation
occurs randomly in space and time. The mean nucleation
time t̄n and the corresponding 2D nucleation rate J can
be obtained from the statistical analysis of experimental
results.
With increasing |Z|, the nucleation rate J increases
much faster than the propagation rate Vp and t̄n becomes
much shorter than tp ðt̄n {tp Þ. In this case the deposition
of each monolayer involves the formation of large
number of nuclei. During the growth process the growth
morphology of the crystal face has a multilevel structure,
which is formed due to the nucleation occurring on top
of growing 2D islands of the preceding monolayer. This
multinuclear multilayer growth has been investigated
extensively by different analytical methods and Monte
20
i (mA cm2)
10
0 10 20 30 40
50
t (ms)
Figure 5 Current density transient for the multinuclear
multilayer growth of a quasi-perfect (screw dislocation–free)
Ag(100) single crystal face at an overpotential. Adapted from
Budevski E, Obretenov W, Bostanov V, et al. (1989) Noise
analysis in metal deposition – Expectations and limits.
Electrochimica Acta 34: 1023–1029.
Carlo simulations using various approximations. Ac-
cording to the theoretical calculations, the overall tran-
sient is characterized by an initial current increase
followed by several oscillations before reaching the
steady-state current density given by
jiss j ¼ bqmon ðbJVp2 Þ1=3 ½14
where b is a constant, which varies from theory to theory
and has a value close to unity.
Figure 5 presents a typical experimental current
transient obtained on a screw dislocation–free Ag(100)
½13 face at an overpotential Z ¼  14 mV. As seen, the tran-
sient shows the characteristic current oscillations pre-
dicted by the theoretical calculations for the case of
multinuclear multilayer growth. The product ðbJVp2 Þ can
be evaluated from the very initial rising part of the cur-
rent transient, which is described by jiðt Þj ¼ jqmon jbJVp2 t 2.
The analysis of experimental data for |iss| and ðbJVp2 Þ
obtained at different Z in an ln |iss| versus ln ðbJVp2 Þ plot
shows a linear dependence with a slope of 1/3 in good
agreement with eqn [14].
The growth mechanisms with 2D nucleation dis-
cussed above operate rarely in real systems because real
crystals are usually not perfect and contain screw dis-
locations. It is well known that screw dislocations play an
important role in determining the mechanism of growth
of real crystals. A screw dislocation intersecting a singular
crystal face gives rise to the appearance of a step, which
originates from the intersection point (Figure 6(a)). After
application of a cathodic overpotential, this step winds up
into a spiral and the growth takes place by the so-called
spiral growth mechanism (Figure 6(b)). A specific feature
of this mechanism is that during the growth process, the
spiral step does not disappear and the crystal face can

grow continuously even at very low |Z| without the need
of 2D nucleation. The height of spiral steps is related to
the Burgers vector of screw dislocation and for metal
crystals is usually equal to the height of the monatomic
steps. The growth spirals consisting of monatomic steps
appear as growth pyramids with a slope determined by
the step distance (the distance between spiral turns) ds(Z).
At low cathodic overpotentials |Z|{kBT/ze the steady-
state current density for the spiral growth is given by
2 boundaries, the initial growth current I(t) is described by
Vp ðZÞ qmon kV 2
jiss j ¼ qmon ¼ Z
ds ðZÞ 19e
where e is the specific edge energy and kV the propa-
gation rate constant of monatomic steps defined by
kV ¼ Vp(Z)/|Z|. The parabolic |iss|  Z2 dependence
predicted by eqn [15] has been found experimentally by
electrochemical growth of ‘quasi-perfect’ Ag(100) and
Ag(111) crystal faces with limited number of screw dis-
locations. As seen from eqn [15], the steady-state current
density iss does not depend on the number density Nd of
screw dislocations intersecting the crystal face. On the
contrary, the current density transient i(t) for the spiral
growth depends on Nd and can be expressed by the
equation
iðt Þ ¼ ið0ÞexpðNd bVp2 t 2 Þ
þ iss ½1  expðNd bVp2 t 2 Þ
(a) (b)
Figure 6 Schematic representation of the spiral growth
mechanism: (a) crystal face with a step originating from a screw
dislocation and (b) spiral growth of the crystal face.
1.0
0.8
I (A)
0.6
0.4
0.2
0 5 10
(a) t (s)
Figure 7 Current transient for the spiral growth of a Ag(111) crystal face intersected by only one screw dislocation (initial overpotential
|Zi| ¼ 0.25 mV; final overpotential |Zf| ¼ 1.15 mV ) (a) overall current transient and (b) I vs t 2 plot of the initial part of the transient. Adapted
from Staikov G, Obretenov W, Bostanov V, Budevski E, and Bort H (1980) Current transients for the electrolytic growth of crystal faces
intersected by screw dislocations. Electrochimica Acta 25: 1619–1623.
Electrochemical Theory | Electrocrystalization 37
where i(0) represents the current density at t ¼ 0. This
current–time relationship is derived on the basis of
Kolmogorov–Avrami relation (eqn [8]) considering a
large number of dislocations randomly distributed on the
crystal face.
Figure 7(a) shows a current transient obtained on a
‘quasi-perfect’ Ag(111) crystal face intersected by only
one screw dislocation. At short times, before the inter-
ference of the new growth pyramid with the face
½15
I ðt Þ ¼ I ð0Þ þ ½iss  ið0ÞbVp2 t 2 ½17
where I(0) and i(0) ¼ I(0)/A are the current and the
current density at t ¼ 0. Figure 7(b) represents the initial
part of experimental current transient in an I versus t 2
plot. From the analysis of observed linear I  t 2 de-
pendence and from the steady-state current obtained at
long times, the parameters (kV and e) characterizing the
spiral growth process can be determined.
Electrocrystallization Processes Relevant
to the Lead–Acid Battery System
½16 As mentioned in the ‘Introduction’ section, the electro-
chemical reactions occurring during the operation of the
lead–acid battery involve the formation of nonmetallic
crystal phases such as the semiconducting lead dioxide
and the insulating lead sulfate. The investigation of
kinetics and mechanism of these electrocrystallization
processes under real operation conditions of the lead–
acid battery is a very difficult task. An effective approach
to overcome some of the arising problems is described in
this section. This approach is based on the application of
microelectrodes and allows the study of nucleation and
growth kinetics of single growth centers of the new 3D
0.5
0.45
I (A)
0.4
0.35
15 20 0 4 8 12
(b) t 2 (s2)
38 Electrochemical Theory | Electrocrystalization

12 •
3
•
10 •
•
•

I 1/2 (nA1/2)
8 2
•

I (nA)
6 •
•
•
4 1 •
•
2 t0 •
•

0
0 40 80 120 20 40 60 80
(a) t (s) (b) t − t 0 (s)

Figure 8 Current transient for the electrocrystallization of a-PbO2 on a carbon disk microelectrode (radius 4 mm) at an overpotential
Z ¼ 400 mV: (a) I vs t transient and (b) I1/2 versus (t  t0) plot of the transient. Adapted from Li LJ, Fleischmann M, and Peter LM (1989)
Microelectrode studies of lead–acid battery electrochemistry. Electrochimica Acta 34: 459–474.

crystal phase by electrochemical and microscopic
measurements.
Figure 8 shows a typical current transient obtained
during anodic electrocrystallization of a-PbO2 on a
carbon disk microelectrode with a 4 mm radius. The
corresponding electrochemical reaction is given by
Pb2þ þ 2H2 O-PbO2 þ 2e þ 4Hþ
the birth of the first nucleus t0 by analyzing sufficient
number of nucleation events at different overpotentials.
Carbon microelectrodes modified with electrodeposited
single lead dioxide centers were also applied successfully
for investigation of the reductive transformation of
lead dioxide to lead sulfate in sulfuric acid electrolyte
solutions.
½II

The driving force for this electrocrystallization process is Conclusions

given by the anodic overpotential Z ¼ E  E3DPbO2 > 0
where E3DPbO2 represents the Nernst equilibrium po-
tential of the 3D lead dioxide phase. As seen in
Figure 8(a), after application of the overpotential at t ¼ 0
a sharp current increase is observed at a relatively long
time t0 corresponding to the birth of the first stable
growth center of lead dioxide. Figure 8(b) shows that the
initial rising part of the transient in Figure 8(a) is in
agreement with the current–time relation for kinetically
(charge transfer) controlled growth of a single hemi-
spherical lead dioxide center given by
nF 3
I ðt Þ ¼ 2p V ðt  t0 Þ2
vM g
In this equation, n ¼ 2 is the number of transferred
electrons, F the Faraday number, vM the molar volume of
the lead dioxide deposit, and Vg ¼ Vg(Z) the overpotential
dependent growth rate. The deviation from the linear
I1/2 versus (t  t0) plot at (t  t0) > 40 s observed in
Figure 8(b) is due to the birth of a second lead dioxide
growth center. Subsequent examination of lead dioxide
deposit by scanning electron microscopy (SEM) con-
firmed the formation of a second growth center. SEM
studies also confirmed the hemispherical shape of the
growing centers. From the slopes of experimental linear
I1/2 versus (t  t0) plots and eqn [18], the overpotential
dependence of the growth rate Vg(Z) was determined.
The nucleation rate can be extracted from the times for
This article reviews the present knowledge of nucleation
and crystal growth phenomena involved in electro-
crystallization. The theory and experiment of electro-
chemical nucleation have been well developed. A
significant contribution has been made by the intro-
duction of the atomistic nucleation theory. The mech-
anisms and kinetics of crystal growth are well understood
and have been experimentally verified in the case of
electrocrystallization of silver on isolated silver single-
crystal faces. Although the considerations in this article
are restricted to the simple case of electrocrystallization
of metals, the presented basic theoretical and experi-
½18 mental concepts are general and can be applied to other
electrocrystallization systems. In real systems, however,
and in particular in the battery systems electro-
crystallization processes are complex and are often
coupled to other electrochemical and chemical rea-
ctions. Therefore, developments of specific sophisticated
experiments and theoretical models are necessary to
elucidate the kinetics and mechanism of electrocry-
stallization.
Nomenclature
Symbols and Units
A area of a crystal face
B,b geometrical factors
 Electrochemical Theory | Electrocrystalization 39

c concentration of metal ions in the Abbreviations and Acronyms

electrolyte 2D two-dimensional
ds step distance SEM scanning electron microscopy
D diffusion coefficient of metal ions in the UPD underpotential deposition
electrolyte
e elementary charge
E electrode potential
E3DMe equilibrium potential of a 3D metal
See Also: Chemistry, Electrochemistry, and
phase
Electrochemical Applications: Lead; Silver;
fmon frequency of generation of monolayers
Electrochemical Theory: Electrokinetics; Kinetics;
F Faraday number
History: Electrochemistry; Recycling: Lead–Acid
i current density
Batteries: Overview; Secondary Batteries – Lead–Acid
i¯ mean current density
Systems: Overview.
iss steady-state current density
I current
J stationary nucleation rate
Further Reading
K1, K10 preexponential factors in nucleation
rate equations Armstrong RD and Harrison JA (1969) Two-dimensional nucleation in
K2 nucleation constant electrocrystallization. Journal of the Electrochemical Society 116:
kB Boltzmann constant 328--331.
Bockris JO’M and Despic AR (1970) The mechanism of deposition and
Kd growth constant dissolution of metals. In: Eyring H, Henderson D, and Jost W (eds.)
n number of atoms in a metal cluster Physical Chemistry – An Advanced Treatise, vol. IXB, pp. 611--730.
nc number of atoms in a nucleus New York: Academic Press.
Bockris JO’M and Razumney GA (1967) Fundamental Aspects of
N number density of nuclei Electrocrystallization. New York: Plenum Press.
N0 number density of nucleation sites Bostanov V, Staikov G, and Roe DK (1975) Rate of propagation of
Nd number density of screw dislocations growth layers on cubic crystal faces in electrocrystallization of silver.
Journal of the Electrochemical Society 122: 1301--1305.
t time (nucleation pulse duration) Budevski E (1983) Deposition and dissolution of metals and alloys. Part
T temperature A: Electrocrystallization. In: Conway EB, Bockris JO’M, Yeager E,
vm volume of an atom in the crystal phase Khan SUM, and White RE (eds.) Comprehensive Treatise of
Electrochemistry, vol. 7, pp. 399--450. New York and London:
Vg overpotential-dependent growth rate Plenum Press.
Vp rate of propagation of monatomic steps Budevski E, Bostanov V, and Staikov G (1980) Electrocrystallization.
qmon charge density needed for deposition of Annual Review of Material Science 10: 85--112.
Budevski E, Staikov G, and Lorenz WJ (1996) Electrochemical
one monolayer Nucleation and Growth: An Introduction to the Initial Stages of Metal
z charge number Deposition. Weinheim: VCH.
DG̃ energy of formation of a metal cluster Budevski E, Staikov G, and Lorenz WJ (2000) Electrocrystallization:
Nucleation and growth phenomena. Electrochimica Acta 45:
Dl̃ supersaturation 2559--2574.
e specific edge energy of monatomic Fischer H (1954) Elektrolytische Abscheidung und Elektrokristallisation
steps von Metallen. Berlin: Springer.
Fischer H (1969) Electrocrystallization of metals under ideal and real
g overpotential conditions. Angewandte Chemie 8: 108--119.
gcrit critical overpotential Fleischmann M and Thirsk HR (1960) Anodic electrocrystallization.
h actual fractional surface coverage Electrochimica Acta 2: 22--49.
Fleischmann M and Thirsk HR (1963) Metal deposition and
hext extended fractional surface coverage electrocrystallization. In: Delahay P (ed.) Advances of
jv propagation rate constant of Electrochemistry and Electrochemical Engineering, vol. 3,
monatomic steps pp. 123--210. New York: John Wiley & Sons.
Fleischmann M, Pons S, Sousa J, and Ghoroghchian J (1994)
r average surface energy of a nucleus Electrodeposition and electrocatalysis – The deposition and
s̄n mean nucleation time dissolution of single catalyst centers. Journal of Electroanalytical
sp mean propagation time Chemistry 366: 171--190.
Harrison JA, Rangarajan SK, and Thirsk HR (1966) Some problems of
/i binding energy of an atom in the i th electrodeposition. Journal of the Electrochemical Society 113:
position of a cluster 1120--1129.
/k binding energy of an atom in a kink-site Harrison JA and Thirsk HR (1971) The fundamentals of metal
deposition. In: Bard AJ (ed.) Electroanalytical Chemistry, vol. 5,
position pp. 67--148. New York: Marcel Dekker.
U energy excess connected with the Kaischew R and Budevski E (1967) Surface processes in
creation of new interfaces electrocrystallization. Contemporary Physics 8: 489--516.
Li LJ, Fleischmann M, and Peter LM (1989) Microelectrode studies of
U* factor accounting for the nucleus– lead–acid battery electrochemistry. Electrochimica Acta 34:
substrate interaction 459--474.
40 Electrochemical Theory | Electrocrystalization
Milchev A (1991) Electrochemical phase formation on a foreign
substrate – basic theoretical concepts and some experimental
results. Contemporary Physics 32: 321--332.
Milchev A (2002) Electrocrystallization: Fundamentals of Nucleation and
Growth. Boston/Dordrecht/London: Kluwer Academic Publishers.
Paunovic M and Schlesinger M (1998) Fundamentals of
Electrochemical Deposition. New York: Wiley-Interscience.
Scharifker B and Hills G (1982) Theoretical and experimental studies of
multiple nucleation. Electrochimica Acta 28: 879--889.
Staikov G (1995) Fundamentals of electrodeposition of metals.
In: Gewirth AA and Siegenthaler H (eds.) Nanoscale Probes of Solid/
Liquid Interface, pp. 193--213. Dordrecht/Boston/London: Kluwer
Academic Publishers.
Staikov G (2002) Nucleation and growth in microsystem echnology.
In: Schultze JW, Osaka T, and Datta M (eds.) Electrochemical
Microsystem Technologies, pp. 156--184. London and New York:
Taylor & Francis.
Staikov G, Lorenz WJ, and Budevski E (1999) Low-dimensional metal
phases and nanostructuring of solid surfaces. In: Lipkowski J and
Ross PN (eds.) Imaging of Surfaces and Interfaces, pp. 1--56. New
York: Wiley-VCH.
Staikov G and Milchev A (2007) The impact of electrocrystallization on
nanotechnology. In: Staikov G (ed.) Electrocrystallization in
Nanotechnology, pp. 3--29. Weinheim: Wiley-VCH.
Thirsk HR and Harrison JA (1972) A Guide to the Study of Electrode
Kinetics. New York: Academic Press.
Vetter K (1967) Electrochemical Kinetics. New York: Academic Press.
Volmer M (1939) Kinetik der Phasenbildung. Leipzig/Dresden: Teodor
Steinkopf.
Walsh FC and Herron ME (1991) Electrocrystallization and electro-
chemical control of crystal growth: Fundamental considerations
and electrodeposition of metals. Journal of Physics D: Applied
Physics 24: 217--225.