Electrodeposition of PbSe onto n-Si(1 0 0) wafers

Article abstract of DOI:10.1016/j.electacta.2007.12.066

PbSe was electrodeposited onto monocrystalline n-Si(1 0 0) wafers from 50 mM Pb(NO₃)₂ + 2 mM SeO₂ + 0.1 M HNO₃ solution. The mechanism of PbSe electrocrystallization on n-Si was studied. At initial stage, 3D Pb and 3D Se nuclei are simultaneously codeposited onto Si at potentials more negative than Si flat band potential and chemically interact resulting in PbSe formation. When n-Si/PbSe heterostructure is formed, the overvoltage of bulk lead deposition increases, as a result of redistribution of electrode potential. Further growth of PbSe is realized due to underpotential deposition (UPD) of Pb and overpotential deposition (OPD) of Se onto formed PbSe nuclei. With Pb UPD shift increase, amorphous Se inclusion is registrated in the deposit. When 2D Pb nucleation mechanism is changed to 3D mode, metal Pb cubic phase is codeposited with PbSe. Electrodeposition of PbSe onto n-Si is irreversible. PbSe anodic stripping does not take place in the dark due to the barrier on solid interface. Oxidation of PbSe on n-Si is observed only under illumination, when photoholes are generated in silicon substrate.

Full text of DOI:10.1016/j.electacta.2007.12.066

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Electrochimica Acta 53 (2008) 5051–5057
Electrodeposition of PbSe onto n-Si(1 0 0) wafers
Yu.A. Ivanova, D.K. Ivanou, E.A. Streltsov∗
Belarusian State University, Chemistry Department, Leningradskaya Street 14, 220030 Minsk, Belarus
Received 18 September 2007; received in revised form 14 November 2007; accepted 23 December 2007
Available online 6 January 2008
Abstract
PbSe was electrodeposited onto monocrystalline n-Si(1 0 0) wafers from 50 mM Pb(NO3)2 + 2 mM SeO2 + 0.1 M HNO3 solution. The mechanism
of PbSe electrocrystallization on n-Si was studied. At initial stage, 3D Pb and 3D Se nuclei are simultaneously codeposited onto Si at potentials more
negative than Si flat band potential and chemically interact resulting in PbSe formation. When n-Si/PbSe heterostructure is formed, the overvoltage of
bulk lead deposition increases, as a result of redistribution of electrode potential. Further growth of PbSe is realized due to underpotential deposition
(UPD) of Pb and overpotential deposition (OPD) of Se onto formed PbSe nuclei. With Pb UPD shift increase, amorphous Se inclusion is registrated
in the deposit. When 2D Pb nucleation mechanism is changed to 3D mode, metal Pb cubic phase is codeposited with PbSe. Electrodeposition of
PbSe onto n-Si is irreversible. PbSe anodic stripping does not take place in the dark due to the barrier on solid interface. Oxidation of PbSe on n-Si
is observed only under illumination, when photoholes are generated in silicon substrate.
© 2008 Published by Elsevier Ltd.
Keywords: PbSe; Electrodeposition; Silicon; UPD; Photoelectrochemistry
1. Introduction
Only two papers are devoted to the electrochemical depo-
sition of PbSe onto monocrystalline silicon [73,74], where
monocrystalline p-Si(1 0 0) wafers were used. Other papers are
dedicated to PbSe electrosynthesis on metal substrates (Ti, Pt,
Au) [75–80,63], conducting SnO2 on glass [81,82], monocrys-
talline InP [52,53].
As shown in our preceding studies [76–79] PbSe electrode-
position onto metal substrates (Au, Pt) can be realized from the
ordinary acidic electrolyte containing Pb(NO3)2 and SeO2. We
have proved that polycrystalline PbSe films as well as PbSe
nanoparticles in Se matrix could be obtained. The potential
applied and the composition of the electrolyte were found to
be the critical factors determining substructure and composition
of a product.
Bulk PbSe has cubic crystal structure (rock salt,
a = 0.61224 nm). It is a narrow direct band gap semiconduc-
tor (Eg = 0.28 eV at 300 K at the L point of the Brillouin zone
[1]). It has been mainly used for infrared emitters, detectors,
laser diodes and thermovoltaic energy converters manufactur-
ing [2–6]. Great attention has been paid to the investigation
of the quantum size dependent properties of PbSe and devel-
oping of methods for PbSe nanoparticles producing [1,7–24].
PbSe deposition onto the surface of Si with the formation of
Si/PbSe heterostructures is of great interest from the practical
point of view because silicon is a basic material for modern
electronics. Si/PbSe heterostructures are produced by differ-
ent methods including MBE [25–27], thermal evaporation in
vacuum [3], liquid-phase epitaxy [28], pulsed laser deposition
[29], etc.
PbSe electrosynthesis should be carried out at potentials
E slightly more positive than equilibrium potential EPb2+
/Pb0
(E < EPb2+
). In this case electrosynthesis of PbSe occurs
/Pb0
Electrodeposition is a promising method for synthesis of
semiconductor polycrystalline films [30–44], epitaxy films
[45–54], heterostructures [55–60], superlattices and multilayer
structures [61–67], nanoparticles [68–72], etc.
due to chemical interaction of codeposited Se (OPD) and Pb
(UPD) [76–79]. If the potential E is several millivolt more pos-
itive than EPb2+
, the surface coverage of Pbad on Se (θ)
/Pb0
reaches its maximum value, causing the deposition of lead and
selenium atoms in 1:1 ratio. So, PbSe with a composition close
to the stoichiometric is formed. At potentials 100–300 mV, being
∗
more positive than EPb2+
, the value θ decreases and the
/Pb0
Corresponding author. Tel.: +375 17 2095178; fax: +375 17 2264696.
product contains PbSe and a portion of amorphous Se.
E-mail address: streltea@bsu.by (E.A. Streltsov).
0013-4686/$ – see front matter © 2008 Published by Elsevier Ltd.
doi:10.1016/j.electacta.2007.12.066

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Yu.A. Ivanova et al. / Electrochimica Acta 53 (2008) 5051–5057
The present work is focused on the mechanism of PbSe
electrodeposition onto monocrystalline n-Si(1 0 0) wafers and
charge transport in n-Si/PbSe/electrolyte system.
microscope (ROENTEC GmbH). X-ray diffraction (XRD) study
was carried out with an HZG-4A diffractometer using Co K␣
radiation (Fe filter).
2. Experimental
3. Results and discussion
PbSe was electrochemically deposited onto the surface of
monocrystalline n-Si(1 0 0) wafers (P-doped with resistivity of
4.5 ꢀ cm). Electrical contact to the substrates was performed
through In-Ga eutectic. Prior to electrochemical experiments,
Si substrates were subsequently cleaned in 56 wt.% nitric acid
at 80 ◦C during 30 s, washed by bidistilled water and etched in
4 wt.% hydrofluoric acid to remove the native surface oxide and
to form atomically smooth H-terminated surface.
Electrochemical and photoelectrochemical measurements
were carried out in a three-electrode two-compartment cell
(20 cm3) with an optical quality window, platinum counter-
electrode and Ag,AgCl|KCl(sat.) reference electrode (+0.220 V
vs. SHE). All potentials are given further with respect to
this electrode. The potentials were controlled by the conven-
tional programmable potentiostat. The potential scan rate was
0.02 V s−1 in all potentiodynamic experiments. The electrolytes
were prepared using high purity reagents and bidistilled water.
The deposition was carried out at constant temperature of
20 2 ◦C.
3.1. Electrodeposition of PbSe onto n-Si. The effect of
potential on phase composition and substructure of deposit
Fig. 1a represents voltammogram for n-Si electrode in solu-
tion for PbSe deposition. From Fig. 1b, which represents
current–timecurves, itisclearthatthedensityofcathodiccurrent
is negligible (∼7–15 ␮A/cm2) at E = −0.385 V (this potential
was applied for PbSe deposition onto Au and Pt [76–79]) and
does not allow to form uniform deposits on n-Si substrate. There-
fore, we applied more negative potentials within the range from
−0.41 to −0.47 V. At the initial stage of deposition the cur-
rent increases sharply and then takes constant value (Fig. 1b).
At these potentials the density of cathodic current is signifi-
cantly higher than at E = −0.385 V and the uniform coatings on
Si surface could be produced.
Typical SEM patterns of deposits obtained within the poten-
tial range from −0.41 to −0.47 V are presented in Fig. 2. As
seen the deposition potential determines the product morphol-
ogy. The deposit obtained at E = −0.41 V (Fig. 2a) consists
of two types of substructures: numerous roundish separated
and assembled particles of 30–50 nm size and some spheri-
cal particles with diameters of 200–380 nm. The EDX analysis
shows that Se is mainly concentrated in big separate spheri-
cal particles all over the deposit. The element ratio Pb:Se is
0.43:1 and 0.08:1 for these two types of structures, respec-
tively. XRD data point to only cubic PbSe phase. The excess
of Se (in addition to PbSe) detected in the film by EDX does
not appear on XRD patterns and represents an amorphous form
which is typical for Se electrodeposited at ambient conditions
[79,83].
Before electrochemical experiments the electrolytes were
deaerated by Ar during 10 min. During all the experiments Ar
flow was kept above the electrolyte in the cell. The halogen lamp
(50 W, 12 V) with IR filter was used as a light source. The light
flux power J = 7 mW cm−2
.
Si/PbSe and Si/Se electrodes were prepared by electrode-
position of PbSe and Se onto n-Si wafers from 50 mM
Pb(NO3)2 + 2 mM SeO2 + 0.1 M HNO3 and 2 mM SeO2 + 0.1 M
HNO3 solutions at potentials −0.43 and −0.50 V, respectively.
Scanning electron microscopy (SEM) and energy dispersive
X-ray (EDX) investigations were performed with an LEO 1455
Fig. 1. Cyclic voltammogram (a) and current–time transients (b) for PbSe deposition onto n-Si from 50 mM Pb(NO3)2 + 2 mM SeO2 + 0.1 M HNO3 electrolyte at
different potentials: E = −0.385 V (1), E = −0.41 V (2), E = −0.43 V (3), E = −0.45 V (4) and E = −0.47 V (5).

Yu.A. Ivanova et al. / Electrochimica Acta 53 (2008) 5051–5057
5053
Fig. 2. SEM patterns of deposits obtained on n-Si by electrodeposition from 0.1 M HNO3 + 50 mM Pb(NO3)2 + 2 mM SeO2 electrolyte at different potentials:
E = −0.41 V (a), E = −0.43 V (b), E = −0.45 V (c) and E = −0.47 V (d).
Fig. 2b and c shows that the deposits obtained at E = −0.45 V
and E = −0.43 V constitute uniform coatings of particles with
well-identified cubic shape and particle size of 50–130 nm. The
element ratio Pb:Se is found to be 0.95:1 and 0.96:1 in these
samples, respectively. Bothdepositscontainonlypolycrystalline
PbSe.
On the SEM image of the sample obtained at E = −0.47 V
(Fig. 2d) particles with sizes of 40–100 nm are observed. The
XRD data indicate two phases in this deposit: cubic PbSe and
cubic Pb (a = 0.4951 nm). Element Pb:Se ratio is 1.1:1.
Thus, PbSe phase was formed in all deposits in the poten-
tial range from −0.41 to −0.47 V. However, monophase PbSe
deposit with element ratio close to stoichiometric was formed in
rather narrow potential range from −0.43 to −0.45 V. At more
negative potentials bulk lead is also crystallized, but at more
positive amorphous Se is also formed. Thus, electrosynthesis of
PbSe on n-Si takes place at more negative potentials than on
a metal substrate. Electrochemical deposition of Pb and Se on
n-Si has been investigated to elucidate the peculiarities of PbSe
electrodeposition onto n-Si.
Our results on Pb deposition onto n-Si (Fig. 3a) are in good
agreement with their study [84]. In the acidic Pb(II)-containing
electrolyte, lead deposition onto n-Si is observed at potentials
E ≤ −0.41 V with small overvoltage (ηc = 0.02 V). The flat band
potential (Efb) of silicon is −0.3 V in 0.1 M HNO3 [85], so Pb
deposition proceeds below Efb (Si) and the overvoltage can be
related to the nucleation barrier. Lead anodic stripping takes
place above −0.39 V with no overvoltage (Fig. 3a, anodic peak
B) indicating the absence of a barrier on n-Si/Pb interface
[84].
In Se(IV) containing solution, the cathodic current on
n-Si appears at E ≤ −0.4 V (Fig. 3b) and is related to
Se(IV) reduction on Si substrate which occurs with a rather
high cathodic overvoltage ηc = 0.92 V (ESe(IV)/Se(0) = +0.52).
A high cathodic overvoltage was also observed in Te elec-
trodeposition onto n-Si [85]. Such electrochemical behavior
is typical of systems with EOx/Red located in the band
gap of semiconductor and is attributed to the space charge
region (SCR) formation in n-Si at E > Efb. Indeed, in the
solution containing different redox systems such as I3−/I−
−
(EI
= +0.33 V) and Fe3+/Fe2+ (EFe3+
= +0.25 V),
/Fe2+
3 /I−
cathodic currents on Si electrode appear below −0.30 and
−0.15 V, respectively (Fig. 3c). The overvoltage ηc = 0.66 V
for I3−/I− and ηc = 0.40 for Fe3+/Fe2+ redox system. Krumm
et al. have also observed high overvoltage for metal reduc-
3.2. Electrochemical deposition of Pb and Se onto n-Si. The
origin of overvoltage of Pb and Se deposition
Lead electrodeposition onto n-Si was studied earlier by
Staikov and coworkers [84], who have shown that deposition
occurred with overvoltage. No Pb UPD proceeded onto Si
because of weak metal–substrate interaction. The nucleation
conformed to the progressive model with the critical nuclei of
11 1 atoms [84].
tion on n-Si(1 1 1) in the case when EMen+
[86].
ꢀ Efb
/Me0
Selenium electrodeposited onto Si does not undergo anodic
oxidation in the dark and under illumination as well. This fact
can be explained based on band model. The band discontinuity

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Yu.A. Ivanova et al. / Electrochimica Acta 53 (2008) 5051–5057
reasons for the lack of Pb particles on Si surface are discussed
below.
Electrodeposition is localized on silicon surface only in the
initial stage. In the course of PbSe and Se nucleation, n-Si/PbSe
and n-Si/Se heterostructures are formed, which affect the charge
transport in the system and the further nucleation process. In this
connection, we have studied the electrochemical behavior of n-
Si/PbSe and n-Si/Se electrodes and compared it with processes
on Au/PbSe.
3.3. Cathodic deposition of lead onto n-Si/PbSe and
n-Si/Se heterostructures
Fig. 4a presents the voltammograms for Au/PbSe electrode in
0.05 M Pb(NO3)2 + 0.1 M HNO3 solution. Electrochemical pro-
cesses on Au/PbSe electrode in Pb(II)-containing solution were
investigated in detail earlier[88]. CathodicpeakC at E < +0.04 V
is related to lead UPD (Pbad) onto PbSe. At E < −0.41 V, the
cathodic current increases due to bulk lead deposition (Pbbulk).
InthereversepotentialscantheanodicdissolutionofPbbulk takes
place at E > −0.39 V (anodic peak B) and Pbad stripping occurs
Fig. 3. Voltammograms for n-Si(1 0 0) electrode in 0.1 M HNO3 (a, dotted line),
0.1 M HNO3 + 50 mM Pb(NO3)2 (a, solid line); 0.1 M HNO3 + 2 mM SeO2 (b);
1 mM I2 + 0.1 M KI (c, dotted line); 0.05 M K3[Fe(CN)6] + 0.05 M K4[Fe(CN)6]
(c, solid line) electrolytes, recorded in the dark. The arrows indicate the equi-
librium potentials for redox systems used.
is formed on the n-Si/Se interface and prevents charge transport
through Si/Se interface [87].
Thus, the cathodic current onsets on n-Si in electrolytes, con-
taining Se(IV) and Pb(II), are observed at practically the same
potential −0.4 V. Both the deposition of metal and chalcogen
proceed with overvoltages. However, the values of the over-
voltages and their origin are different. Small overvoltage of Pb
deposition is caused by the nucleation barrier, while high over-
voltage of Se deposition is related to the SCR formation in n-Si
above Efb.
It should be noted that anodic peak of Pbbulk oxidation is
absent on voltammogram of n-Si electrode in solution contain-
ing both Pb(II) and Se(IV) species after cathodic potential scan
(Fig. 1a) indicating the lack of 3D Pb nuclei on Si surface. This is
due to the chemical interaction of codeposited Pb and Se. Other
Fig. 4. Cyclic voltammograms for Au/PbSe (a) and for n-Si/PbSe electrode,
recorded in the dark (b) and under illumination (c) in 0.1 M HNO3 + 50 mM
Pb(NO3)2 electrolyte.

Yu.A. Ivanova et al. / Electrochimica Acta 53 (2008) 5051–5057
5055
at E > +0.1 V (anodic peak A). Illumination does not effect these
processes because PbSe is photoelectrochemically non-active.
As regards to n-Si/PbSe heterostructure, cathodic deposi-
tion of both Pbad and Pbbulk occurs at more negative potentials
compared with Au/PbSe. Lead UPD (peak C1) takes place at
potentials E ≤ −0.20 V and bulk lead deposition is observed
at potentials E ≤ −0.47 V (Fig. 4b). The overvoltage of Pbbulk
deposition onto n-Si/PbSe (ηc = 0.08 V) is higher compared with
the deposition on Au/PbSe (ηc = 0.02 V). Anodic oxidation of
Pbbulk (B) is observed at E > −0.38 V.
Illumination of n-Si/PbSe electrode does not affect cathodic
processes but affects the anodic processes above Efb (Si). The
peak of anodic stripping of Pbad (A1) is registered only under
illumination at E > −0.22 V (Fig. 4c). The charge corresponding
to peak A1 does not depend on the quantity of electrodeposited
PbSe.
The anodic photocurrent under illumination of n-Si/PbSe
electrode at E > 0.1 V is significantly higher than that for n-Si
substrate (Fig. 4c), and is proportional to PbSe quantity (Fig. 5).
This current is caused by PbSe photooxidation. We did not
observe photoelectrochemical activity of PbSe in experiments
with PbSe electrodeposited on metal substrates (Au, Pt, Ti).
Therefore, we assume that observed photooxidation of PbSe
in n-Si/PbSe occurs due to the photoholes generated in sili-
con substrate. Similar effect was observed also for n-Si/Te [85]
and n-Si/PbTe [89]. In these systems, Te and PbTe (like PbSe)
are photoelectrochemically inactive components. They act as
effective acceptors of photoholes, generated in n-Si substrate,
and contribute to photocurrent increase. Anodic photocurrent
on bare n-Si in 0.1 M HNO3 is caused by silicon photooxidation
resulting in SiO2·nH2O formation.
Fig. 6. Cyclic voltammograms for n-Si/Se electrodes recorded in the dark (a)
and under illumination (b), in 0.05 M Pb(NO3)2 + 0.1 M HNO3 solution. Solid
line corresponds to the first potential scan, dotted line to the second one.
Comparing the voltammograms for Au/PbSe and n-Si/PbSe
in Pb(II)-containing solution, one can conclude that both
cathodic processes on n-Si/PbSe heterostructure and anodic
ones are shifted to more negative values when compared with
Au/PbSe electrode. It is probably related to the potential redis-
tribution in the n-Si/PbSe heterostructure since silicon is a
semiconductor and its resistance is significantly higher than that
of metal. Therefore, in order to obtain PbSe film with compo-
sition close to stoichiometric on n-Si, a more negative potential
should be applied than in PbSe deposition on a metal.
Fig. 6a presents the voltammograms for n-Si/Se electrode
in 0.05 M Pb(NO3)2 + 0.1 M HNO3 solution. Lead UPD onto
n-Si/Se electrode is not observed (both in the dark and under
illumination). In the reverse potential scan, the characteristic
anodic current of bulk lead stripping (Fig. 3a, peak B) is not
registered indicating Pb particles absence on n-Si surface. This
was unexpected because Se electrodeposited onto Si is in the
form of a discontinuous film. The lack of Pb nanoparticles on
Si surface can be related to the chemical interaction between
3D Se and 3D Pb nuclei on Si surface resulting in PbSe. PbSe
formation after bulk lead deposition onto Se was also observed
in our previous work [88] for polycrystalline Se films. As a result
n-Si/Se/PbSe heterostructure is formed. Anodic oxidation of Se
andPbSeisnotobservedinthisthree-componentheterostructure
as the band discontinuity is formed on the interface.
It should be noted that Pb nuclei on Si electrode can be
oxidized by Se(IV) species in the electrolyte. As mentioned
above, the critical size of Pb nuclei on Si corresponds to 11
1
atoms [84], therefore, these small nuclei are very reactive. To
study the possibility of Pb0 oxidation in Se(IV) containing solu-
tion, the lead particles were electrochemically deposited onto
n-Si wafers. Then Si/Pb electrode was immersed into 2 mM
SeO2 + 0.1 M HNO3 solution under open circuit potential for
Fig. 5. Anodic photovoltammograms for n-Si (dotted line) and n-Si/PbSe elec-
trode (solid lines) in 0.1 M HNO3. The charges responsible for cathodic PbSe
deposition are indicated on the plot.

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Yu.A. Ivanova et al. / Electrochimica Acta 53 (2008) 5051–5057
20 min. XRD observation of the product shows the presence
of PbSe on Si/Pb electrode. PbSe is formed according to the
following equation:
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At the illuminated n-Si/Se/PbSe electrode anodic peak
appears above −0.2 V (Fig. 6b). The similar peak is observed
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by Pbad oxidation (the absence of Pbad oxidation current in the
dark is related to the barrier on n-Si/Se/PbSe heterostructure).
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negative potentials due to semiconductor nature of Si. On
silicon, 3D Pb and 3D Se nuclei are simultaneously deposited
and chemically interact resulting in PbSe formation. When
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