Journal of Alloys and Compounds 871 (2021) 159559

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Potential photovoltaic properties of thin film solar cells based on

chemically deposited ZnO/PbSe junctions ]]
]]]]]]
]]

⁎
Simón Roa a, , Myrna Sandoval b, María José Cortés Burgos a, Paulraj Manidurai b, Sergio Suárez c
a
Instituto Balseiro – UNCuyo, Instituto de Nanociencia y Nanotecnología – Centro Atómico Bariloche, CNEA, CONICET, Av. E. Bustillo 9500, R8402AGP San Carlos de
Bariloche, Río Negro, Argentina
b
Departamento de Física, Universidad de Concepción, Víctor Lamas 1290 Casilla 160 C Barrio Universitario, Concepción, Chile
c
División de Colisiones Atómicas, Centro Atómico Bariloche, CNEA, Av. E. Bustillo 9500, R8402AGP San Carlos de Bariloche, Río Negro, Argentina

a r t i cl e i nfo a bstr ac t

Article history: We report for the first time the fabrication of thin film solar cells based only on aqueous-phase chemically
Received 4 February 2021 deposited ZnO/PbSe junctions. In particular, ZnO and PbSe thin films were synthesized by Successive Ionic
Received in revised form 1 March 2021 Layer Absorption-Reaction and Chemical Bath Deposition methods. The photovoltaic performance was
Accepted 15 March 2021
tested by fabricating ITO/ZnO/PbSe/Ag arrangements. Fill factors (FF ), open-circuit voltages (Voc ) and short-
Available online 18 March 2021
circuit current densities ( Jsc ) in the range of 25.4–29.2%, 0.39–0.51 V and 17.9–21.5 mA/cm2 were achieved.
Power conversion efficiencies varied typically between 1.9% and 3.0%. Results showed the important pho­
Keywords:
A. Semiconductors
tovoltaic activity of our solar cells, achieving good and comparable efficiencies to those reported by similar
A. Thin films research. Our research represents a considerable improvement of the cost-performance relation for this
A. Multilayers kind of device.
B. Chemical synthesis © 2021 Elsevier B.V. All rights reserved.
D. Electrical properties

1. Introduction PbSe simple n-p junctions in TFSC technology. Few researchers

ZnO and PbSe are semiconducting materials which present nat­
ural n-type (bandgap (Eg ) = 3.37 eV) [1] and p-type (Eg = 0.27 eV) [2]
conductivities, respectively. ZnO has been considered as an inter­
esting material for different optoelectronic applications, being par­
ticularly attractive for potential applications in Thin Film Solar Cells
(TFSC). In TFSC technology, ZnO thin films have been used as anti-
reflective and Transparent Conductive Oxide (TCO) coatings because
of their high transmittance in the visible range, wide Eg , optimum
refraction index (n ⁓ 2) and n-type conductivity [3–5]. On the other
hand, PbSe has been also considered an attractive material due to its
interesting optoelectronic properties related to quantum size effects.
These effects have been observed for particles (crystals) with sizes
similar or smaller than 46 nm (Bohr exciton radius) [6], enabling to
adjust Eg typically between 0.27 and 1.15 eV [7]. For this reason, the
application of PbSe thin films has extended to simple junction TFSC
designing, where an optimum Eg between 1 and 1.5 eV for the ab­
sorbent layer is required to achieved the highest efficiencies [8].
The semiconducting nature, conductivity type and Eg magnitude
of both compounds have suggested the potential application of ZnO/
⁎
Corresponding author.
E-mail address: sroadaz8@gmail.com (S. Roa).
[9–11] have reported the potential photovoltaic activity of TFSC
based on ZnO/PbSe junctions. Early research on this kind of junctions
was reported by Leschkies [9] who fabricated TFSC based on ITO/
ZnO/PbSe/Au using ZnO and PbSe thin films deposited by using RF
reactive magnetron sputtering and dip-coating methods, respec­
tively. In that case, a power conversion efficiency ( ) of 1.6% was
achieved.
Later research carried out by Semonin [10] based on ITO/ZnO/
PbSe/Au arrangements showed considerable efficiency improve­
ments. Values between 0.7% and 4.5% using thermally evaporated
ZnO and PbSe films grown by dip-coating were achieved. Similar
deposition techniques for synthesizing ZnO/PbSe junctions were
used by Hoye [11] who reported TFSC based on ITO/Zn1−xMgxO/PbSe/
MoO3/Au arrangements. However, ZnO thin films were grown by
using chemical vapor based Atmospheric Atomic Layer Deposition
(AALD) in that case. Similar values to those reported by the pre­
vious authors were obtained by Hoye. An average value of 1.7 ± 0.4%
and a maximum of 2.4% for TFSC based on pure ZnO (x = 0)/PbSe
junctions were achieved. Nevertheless, could be improved up to an
average value of 3.1 ± 0.7% and a maximum value of 3.8% by Mg
doping (x = 0.2).
While Hoye's research about TFSC based on pure ZnO/PbSe
junctions is the most current found in the literature, the record of
4.5% has been reported by Semonin. The common factor of all the

https://doi.org/10.1016/j.jallcom.2021.159559
0925-8388/© 2021 Elsevier B.V. All rights reserved.
S. Roa, M. Sandoval, M.J.C. Burgos et al.
mentioned research [9–11] is that ZnO/PbSe junctions have been
synthesized by using Vapor Phase Deposition (VPD) and APCD
methods for the ZnO and PbSe films synthesis, respectively. In par­
ticular, VPD methods are considerably more expensive and energy-
demanding than the APCD ones. Thus, looking for the cost-perfor­
mance benefits of the TFSC based on ZnO/PbSe junctions, the
synthesis of these junctions by APCD methods is proposed.
Here, we report the successful fabrication of TFSC based only on
aqueous-phase chemically deposited ZnO/PbSe heterojunctions. For
the first time, we present the synthesis of ZnO/PbSe bilayers only
using APCD methods and their potential photovoltaic performance.
Simple and low-cost APCD methods like SILAR [12,13] and CBD
[14–16] methods were particularly used for depositing ZnO and PbSe
thin films, respectively. In general, the photovoltaic performance of
our TFSC based on ZnO/PbSe junctions was comparable concerning
the current reports [9–11], being even better in some cases.
2. Experimental details
2.1. Fabrication of TFSC based on ZnO/PbSe junctions
2.1.1. Substrates cleaning
Indium Tin Oxide (ITO) commercial substrates (In2O3/SnO2,
703192 Sigma-Aldrich®, 1.25 cm × 1.25 cm × 0.11 cm, resistivity:
8–12 Ω/sq) were used to fabricate the ZnO/PbSe junctions. Before
depositing films the substrates were cleaned by rinsing with deio­
nized water and later immersed into a 1:1:1 (vol.) solution of iso­
propanol, acetone and deionized water for 1 day. Then, the
substrates were put into 100 mL of deionized water and placed into
an ultrasonic bath for 30 min. Finally, they were taken out from the
bath, rinsed again with deionized water and dried at room tem­
perature.
2.1.2. Synthesis of ZnO thin films by SILAR method
ZnO thin films were grown on the ITO substrates. Before syn­
thesizing the films, the ITO substrates were masked using a heat
resistant Kapton® tape (heat resistance ⁓280 °C) to grow the ZnO
films on an effective area of 1.25 cm × 0.85 cm ⁓1.06 cm2. The
synthesis process was carried out using the following reagents: Zinc
Sulfate Heptahydrate (ZnSO4 + 7H2O, Sigma-Aldrich®, purity ≥ 99.0%),
Ammonia solution (NH3, EMSURE® 25%), Hydrogen Peroxide (H2O2,
60%) and deionized water.
A room temperature cationic bath (precursor of Zn2+ cations)
consisting of an aqueous solution of 20 mL of ZnSO4 (0.125 M) and
40 mL of NH3 (1.25 M) was used. An initial pH of 11.5 was obtained
for this bath. The considerable excess of NH3 concerning ZnSO4 in
the solution is a necessary condition for the formation of the Zn-
Tetraamine [Zn(NH3)4]2+ complex [17]. On the other hand, an anionic
bath (precursor of O2– anions) consisting of an aqueous solution of
10 mL of H2O2 and 50 mL of deionized water at 75 °C was used.
For the ZnO films synthesis, the masked ITO substrates were
immersed into the cationic bath for 5 s, later immersed into the
anionic bath for 5 s and finally immersed into a cleaning bath (60 mL
of deionized water) for 5 s. A total of 40 immersion cycles (a cycle
involves the mentioned three immersion steps) were used to grow
the ZnO thin films in approximately 10 min. The as-deposited sam­
ples were annealed at 500 °C for 2 h to promote the crystallization of
the films. In particular, a total of three identical ITO/ZnO samples
were synthesized.
The ZnO formation process can be described considering the
following equations which correspond to the cationic bath reac­
tions [17]:
NH3(aq) + H2 O(aq) NH4 OH(aq)
(1)
2
Journal of Alloys and Compounds 871 (2021) 159559
ZnSO4(aq) + 2NH4 OH(aq) Zn (OH)2(s) + (NH4)2SO4(aq).
(2)
An excess of NH4OH produces the complexing effect:
Zn (OH)2(aq) + 4NH4 OH(aq) Zn [(NH3)4 ]2 +(aq) + 4H2 O (aq) + 2OH (aq).
(3)
Consequently, we have the following equations associated with
the anionic bath reactions [17]:
70°C
2H2 O2(aq) 2H2 O(aq) + O2(g) (4)
2Zn [(NH3)4]2+(aq) + 8H2 O(aq) + O2(g) 2ZnO(s) + 8NH4 OH(aq).
(5)
2.1.3. Synthesis of PbSe thin films by CBD
PbSe thin films were synthesized using the following reagents:
Lead Acetate Trihydrate (Pb(C2H3O2)2+3H2O, MERCK®, purity ≥
99.5%), Sodium Hydroxide (NaOH, MERCK®, 99% purity),
Triethanolamine (C6H15NO3 (TEA), MERCK®, purity ≥ 99.5%), Sodium
Sulfite (Na2SO3, Sigma-Aldrich®, purity ≥ 98%), Selenium powder
(Sigma-Aldrich®, purity ≥ 99%) and deionized water. A Sodium
Selenosulfate (Na2SeSO3) solution was prepared to have a stable
selenium anion (Se2–) source. This solution was synthesized by re­
fluxing a solution of 2 g of Selenium powder in 100 mL of Na2SO3
(1 M) at 90 °C for 6 h. A final Na2SeSO3 solution with a concentration
of 0.16 M was obtained.
PbSe thin films were grown on the ITO/ZnO substrates (keeping
the ITO masked area) from an aqueous solution composed of 5 mL of
Pb(C2H3O2)2 (0.2 M), 2.5 mL of TEA (0.4 M), X mL of NaOH (0.2 M),
6.3 mL of Na2SeSO3 (0.16 M) and enough deionized water to fill up a
total volume of 50 mL. The deposition was carried out introducing
the solution into a bath at 70 °C for 1 h. A total of three ITO/ZnO/PbSe
samples were synthesized using X = 11, 12 and 13. A minimum pH of
12.5 was obtained for X = 11. The ITO/ZnO/PbSe samples were la­
beled as A, B and C for X = 13, 12 and 11, respectively.
The growth mechanism associated with the PbSe films deposi­
tion can be described as follows [18,19]:
Pb(2aq+) + C6 H15 NO3(aq) Pb [(C6 H15 NO3)]2(aq
+
) (6)
2
SeSO3( 2
aq) + OH(aq) HSe(aq) + SO4(aq) .
(7)
2+
The Pb[(C6H15NO3)] complex (Eq. 6) originates by the complete
Pb(C2H3O2)2 dissociation (strong electrolyte) into their constituents
ions Pb2+ and CH3COO-. The addition of NaOH and Na2SeSO3 into the
solution produces the Na2SeSO3 dissociation (because it dissociates
in an alkaline medium) decomposing it into the HSe– and SO42– ions
(Eq. 7). An excess of OH– ions, with respect to the HSe– ones, enables
the HSe– dissociation into their constituent ions (H+ and Se2–) by the
H2O formation, which is a more stable compound. Thus, the Pb2+ and
Se2– ions can bond by electrostatic attraction producing a more
stable and neutral compound like PbSe:
Pb [(C6 H15 NO3 )]2(aq
+ + HSe
) (aq) + OH(aq) PbSe(s) + C6 H15 NO3(aq) + H2 O.
(8)
2.1.4. Deposition of Ag electrodes
Ag thin films were grown on the ITO/ZnO/PbSe samples by the
sputtering technique as electrodes for photovoltaic performance
measurements. Films were deposited on an area of 0.8 cm × 0.5 cm
by using a Mini Sputter Coater. An Ar pressure, current and deposi­
tion time of 0.08 mbar, 24 mA and 5 min were used, respectively. A
total of three ITO/ZnO/PbSe/Ag systems were fabricated as simple
junction TFSC.
S. Roa, M. Sandoval, M.J.C. Burgos et al.
2.2. Characterization methods
2.2.1. Structural properties
Thin films structural properties were studied by the X-Ray
Diffraction (XRD) technique. XRD patterns were measured using a
PANALYTICAL Empyrean diffractometer with a k copper X-ray
source (wavelength (λ) = 0.1541 nm). An acceleration voltage and
current of 40 kV and 45 mA were used, respectively. Measurements
were carried out setting a Bragg-Brentano configuration and a 2
scanning range of 20°–80° with a resolution of 0.01°.
2.2.2. Morphological properties
Morphological properties were studied by Scanning Electron
Microscopy (SEM). A SEM-FEI-Nova Nano SEM 230 was used for the
measurements setting a voltage of 5 kV and pressure of 10−7 Torr. A
gold thin film was deposited on each sample using a Mini Sputter
Coater before measuring. An Ar pressure, current and deposition
time of 10−1 mbar, 39 mA and 20 s were used, respectively.
2.2.3. Chemical properties
Chemical composition studies were carried out in a TANDEM-
1.7MV ion accelerator by the Rutherford Backscattering
Spectroscopy (RBS) technique. A α (4He) particles flux of 9.281 × 1010
particles/sr with an energy of 2 MeV was used. Geometry was set to
have incident, exit and scattering angles of 0°, 15° and 165°, re­
spectively. A channel-to-energy calibration parameter of 0.9058 keV/
channel was set. Additionally, films chemical composition was stu­
died by the SEM-assisted Energy Dispersive X-ray Spectroscopy
(EDS) technique. A 20 keV electron beam was used as an excitation
source. EDS spectra analysis was carried out using an EDAX® mi­
croanalysis system.
2.2.4. Optical properties
PbSe films Eg values were estimated by IR spectrophotometry. An
FTIR-MTEC NEXUS 670 spectrophotometer was used to carry out the
transmittance spectra measurements. The spectra were measured in
the Mid Infrared Range (MIR). In particular, wavelengths between
2.5 and 11 µm were considered. ZnO film Eg value was estimated
using a PerkinElmer´s spectrophotometer model LAMBDA35 UV/VIS.
The transmittance spectrum was measured considering the ultra­
violet-visible range (300–800 nm).
2.2.5. Photovoltaic properties
The photo-induced I V response of our TFSC was studied using
a Solar Cells Simulator PET (Photoemission tech, inc.) model
CT80AAA. The I V measurements were carried out considering
voltages between −1 and 1 V with a step of 0.02 V. All measurements
were carried out under the Standard Test Conditions (STC) for solar
cells:
• Irradiance of 0.1 W/cm2 with normal incidence.
• Cell operating temperature close to the room tempera­
ture (25 °C).
• Spectrum radiation with an AM coefficient of 1.5.
3. Results and discussion
3.1. Preliminary studies on the ZnO and PbSe thin films
Preliminary studies on the ZnO and PbSe films were carried out
to ensure good growth quality and adequate optical properties for
applications in TFSC systems. Morphological, structural, optical and
chemical properties were particularly characterized. These proper­
ties were studied in ZnO and PbSe films independently deposited on
soda-lime glass substrates.
3
Journal of Alloys and Compounds 871 (2021) 159559
Fig. 1 shows some SEM images of the ZnO and PbSe thin films,
where the deposition quality can be observed. From the ZnO film
cross-section image (Fig. 1(a)) a clear ZnO-to-substrate interface was
observed, estimating a film thickness of about 130 ± 15 nm. This
considerable thickness dispersion could be associated with the
considerable film superficial roughness. ZnO thin film also presented
a homogeneous and relatively compact microstructure with the
presence of considerable quantities of residual colloids on the sur­
face (see Fig. 1(b)–(d)). The cracks observed in the microstructure
were attributed to the annealing treatment effects. From the PbSe
films cross-section images (example shown in Fig. 1(g)) clear PbSe-
to-substrate interfaces were observed. Films thicknesses of 160 ± 6,
138 ± 9 and 145 ± 7 nm were estimated for X values of 11, 12 and 13,
respectively. PbSe films commonly showed a faceted granular mor­
phology with homogeneous grain sizes and a very compact material
growth (see Fig. 1(h)–(j)). In general, the PbSe films as well as the
ZnO one presented reasonably good growth quality.
XRD results (Fig. 1) showed the polycrystalline nature of the ZnO
and PbSe films. ZnO film presented the characteristic hexagonal
Wurtzite structure following the crystallographic chart JCPDS No.
36-1451 (ZnO Wurtzite powder, cell parameters: a = 3.249 Å and
c = 5.206 Å). In particular, cell parameters a = 3.245 ± 0.002 Å and
c = 5.205 ± 0.002 Å were estimated for the ZnO film. Otherwise, the
PbSe films presented a Halite-like face cubic centered (fcc) structure
following the crystallographic chart JCPDS No. 78-1903 (PbSe
powder, cell parameter: a =6.120 Å). These films particularly pre­
sented a clear preferential orientation growth, showing a pre­
ferred < 100 > texture. Cell parameters of 6.127 ± 0.001,
6.121 ± 0.001 and 6.125 ± 0.001 Å were estimated for X values of 11,
12 and 13, respectively. These parameters were slightly higher but
very close to the corresponding parameter of 6.120 Å indicated by
the JCPDS No. 78-1903 chart. This could be indicating the presence of
tensile strain states developed in the films.
Foreign crystalline phases associated with other possible com­
pounds like PbO or SeO2 were not detected, which confirms the good
structural quality of the PbSe films. Analogously, a similar analysis
can be applied to the ZnO film considering the absence of foreign
crystalline phases associated with possible residual compounds like
Zn(OH)2.
Spectrophotometry measurements (Fig. 1) showed the potential
optical properties of the ZnO and PbSe thin films for TFSC applica­
tions. ZnO thin film particularly showed a good optical transmittance
for wavelengths in the visible range, observing transmittances
higher than 80%. The Eg was found to be in the UVA range
(315–400 nm), estimating a value of 3.23 ± 0.03 eV. While it is ex­
pected that Eg for films is higher than the bulk one because of
quantum confinement effects [20], lower Eg for ZnO films (the op­
posite tendency) have been also reported [13,17]. On the other hand,
the PbSe films absorption edges were identified from the transmit­
tance spectra in Mid-Infrared-Range (MIR). These edges were ob­
served between 3500 and 3750 nm. Consequently, Eg values of
0.329 ± 0.010, 0.326 ± 0.010 and 0.327 ± 0.008 eV were respectively
estimated for X values of 11, 12 and 13. These values imply that, for
wavelengths usually longer than 3750 nm, the transmittance con­
siderably decays because of the appreciable increase of the optical
absorption due to the direct nature of the bandgap transitions. The
direct nature of this transition can be corroborated by observing the
inset graph in Fig. 1(l), where a well-agreement between the Stern
relationship [15] ( h = A (h Eg)n ) and the experimental data at
the absorption edge is achieved by considering n = 1/2 (allowed di­
rect transition). The Stern fits (for n = 1/2) correspond to the extra­
polated solid lines.
Finally, RBS results (see Fig. 2) revealed accurately the growth
quality of the ZnO and PbSe films. From the ZnO film RBS spectrum,
considerable quantities of elements like Zn, Si and O were detected.
A complementary analysis carried out by Proton Induced X-ray
S. Roa, M. Sandoval, M.J.C. Burgos et al. Journal of Alloys and Compounds 871 (2021) 159559

Fig. 1. SEM images of the (a) cross-section and (b–d) different magnifications of the ZnO thin film surface are shown. Also, SEM images of the (g) PbSe film ( X = 11) cross-section
and different images of the PbSe films surfaces with (h) X = 11, (i) X = 12 and (j) X = 13 are shown. Additionally, the (e,k) XRD patterns and (f,l) transmittance spectra corre­
sponding to the ZnO and PbSe films are shown. In all cases, the substrate contributions were subtracted from raw data.

Emission (PIXE) confirmed this fact (see inset graph in Fig. 2(a)). The
presence of important quantities of these elements was expected
because of the film and substrate compositions. Moreover, the pre­
sence of other elements like Na and Ca was also identified but in
relatively low concentrations. Appreciable quantities of these ele­
ments are expected in soda-lime glass substrates [21].
In the RBS spectrum, we observed considerable signals over­
lapping between the characteristic Zn and Si energy loss steps. This
effect was successfully simulated considering intermediate layers at
the ZnO-to-substrate interface with specific concentrations of Zn, Si
and O. This fact could be associated with the presence of important
ZnO interdiffusion into the substrate due to the post-deposition

4
S. Roa, M. Sandoval, M.J.C. Burgos et al.
Fig. 2. RBS spectra of the (a) ZnO and (b) PbSe thin films. Here, the t parameter represents the film thickness calculated by analyzing the RBS spectra. A complementary chemical
analysis of the ZnO film realized by PIXE is shown in the inset graph of (a). A complementary chemical analysis of the PbSe films realized by EDS is shown in the inset graph of (b).
annealing treatment. However, a reasonable estimation of the ZnO
film thickness (120 ± 10 nm) and stoichiometry (atomic concentra­
tion ratio [O]/[Zn] ⁓ 0.9) was achieved. The presence of intrinsic
defects such as O vacancies and Zn interstitials could explain the
observed [O]/[Zn] < 1 [22] ratio. In particular, ZnO with a Wurtzite
structure is naturally an n-type semiconductor because of this kind
of deviation from the ideal stoichiometry [22]. Thus, a possible n-
type behavior could be suggested for our ZnO film.
The PbSe films RBS spectra (see Fig. 2(b)) were successfully
modeled considering a simple film/substrate structure. A substrate
composed of different elements (O, Na, Si and Ca) and thin films with
Se abundance concerning Pb were considered. In general, atomic
concentration ratios [Pb]/[Se] < 1 were estimated for all the PbSe
thin films. Comparing with the ZnO film case it was not necessary to
include interfacial layers in the model, being possible interdiffusion
effects or substrate roughness practically negligible. Results showed
generally well-defined interfaces, which demonstrated the good
quality of the PbSe films growth.
Complementary EDS results (see inset graph in Fig. 2(b)) sup­
ported the previously identified non-stoichiometric nature of the
PbSe films revealing similar tendencies for the ratio [Pb]/[Se]. In
particular, this ratio tended to increase as the NaOH volume ( X )
increased. This tendency could be explained considering some
simple empirical observations. We observed that by introducing
some quantity of NaOH (particularly X =11 mL) into the deposition
solution a visible quantity of “white aggregates” (probably metal-
hydroxide colloids like Pb(OH)2) appeared immediately. This quan­
tity and the precipitation velocity were observed to decrease ap­
preciably as the NaOH volume increased up to 13 mL. Our
observations suggested that the OH– concentration increase inhibits
the formation and early precipitation of metal-hydroxide colloids.
So, the increasing tendency of the [Pb]/[Se] concentration ratio as
the NaOH volume increases could be associated with the decelera­
tion of the Pb(OH)2 colloids precipitation which increases the ef­
fective quantity of Pb2+ ions available for the PbSe films growth. In
synthesis, we observed higher [Pb]/[Se] concentration ratios for
higher NaOH volumes because the Pb2+ abundance in the deposition
solution is higher under that conditions.
The lattice structure of lead chalcogenide compounds may be
very non-stoichiometric [23], as seen in our case. The vacancies and
interstitials can control the conductivity type such that an excess of
5
Journal of Alloys and Compounds 871 (2021) 159559
Pb causes n-type conductivity and an excess of chalcogenide a p-
type conductivity [23,24]. Consequently, a possible p-type behavior
could be suggested for our PbSe thin films.
3.2. Studies on ZnO/PbSe bilayer systems
Fig. 3 shows different characterizations realized for three ZnO/
PbSe bilayers deposited on soda-lime glass substrates (SiO2), being
ZnO the first deposited layer. The difference between each bilayer
system is the parameter X used for the PbSe films deposition.
SEM studies (Fig. 3(a)–(c)) showed the faceted granular mor­
phology of the PbSe films, which was similar to that observed for
those grown on soda-lime glass substrates. In this case, the material
growth was also observed to be pretty compact. A clear increase of
the PbSe films grain sizes was observed concerning those deposited
on soda-lime glass substrates. This considerable grain size increase
could be due to the influence of the ZnO film, which presents grains
considerably larger than those observed for the PbSe ones. ZnO
grains could be acting as seeds for the nucleation of larger PbSe
crystals.
As expected, EDS analysis (Fig. 3(d)–(f)) showed an important
presence of elements like O, Si, Zn, Se and Pb. The presence of Zn, Se
and Pb was associated with the bilayer chemical composition. Also,
light elements like O and Si were associated with the soda-lime glass
substrates as well as the ZnO film. In particular, PbSe films presented
their characteristic ratio [Pb]/[Se] < 1. The non-stoichiometric be­
havior of these films was not critically affected by the substrate
change, referring to the possible p-type or n-type conductivity.
Complementarily, RBS studies enabled us to get similar and con­
sistent conclusions. For example, a characteristic ratio [Pb]/[Se] < 1
was also determined from the RBS spectra for all the PbSe films
deposited on SiO2/ZnO substrates.
Note that the RBS spectra (Fig. 3(g)–(i)) of the SiO2/ZnO/PbSe
systems are fundamentally a superposition of the individual films
and substrates effects (see Section 3.1). Additional effects associated
with non-well-defined ZnO/PbSe interfaces were identified. These
effects were well-modeled considering different interfacial layers
composed of O, Zn, Se and Pb with comparable concentrations. Non-
well-defined ZnO/PbSe interfaces could be associated with the
considerable superficial roughness of the ZnO film (thickness of
130 ± 15 nm). Consequently, a considerable decrease of the PbSe
S. Roa, M. Sandoval, M.J.C. Burgos et al. Journal of Alloys and Compounds 871 (2021) 159559

Fig. 3. SEM images of the ZnO/PbSe bilayers grown on soda-lime glass substrates using X values of (a) 13, (b) 12 and (c) 11. The images correspond to the PbSe films surfaces,
which were deposited on the ZnO films. Under each SEM image the corresponding (d–f) EDS, (g–i) RBS and (j–l) XRD analysis of the samples with X of 13, 12 and 11 are shown,
respectively.

films thicknesses was observed in the bilayer structures (see RBS
spectra in Fig. 3). The thicknesses decreased up to 19% concerning
RBS values estimated for the SiO2/PbSe systems. This decreasing
tendency is a direct consequence of including interfacial effects,
which reduce the effective PbSe film thickness.
XRD results (Fig. 3(j)–(l)) showed the clear presence of the ZnO
and PbSe crystalline phases in the ZnO/PbSe bilayers XRD patterns,
as expected for this case. The same characteristic ZnO hexagonal
Wurtzite and PbSe Halite-like fcc structures were identified. This
evidenced the good structural quality of the PbSe films grown on the

6
S. Roa, M. Sandoval, M.J.C. Burgos et al.
SiO2/ZnO substrates. For all the different bilayers, ZnO films pre­
sented similar cell parameters to that estimated in Section 3.1.
Average cell parameters a = 3.245 ± 0.003 Å and c = 5.203 ± 0.004 Å
were particularly estimated. This is expected since the ZnO films
were grown using the same deposition conditions in all cases. On the
other hand, PbSe films grown on SiO2/ZnO substrates presented
lower cell parameters a than those estimated in the case of the SiO2/
PbSe systems. Values of 6.116 ± 0.001, 6.115 ± 0.001 and
6.118 ± 0.001 Å were estimated for X values of 11, 12 and 13, re­
spectively. In particular, these parameters were slightly lower but
very close to the corresponding parameter of 6.120 Å indicated by
the JCPDS No. 78-1903 chart. This could be indicating the presence of
compressive strain states developed in the films because of the ZnO
films influence.
3.3. Photovoltaic performance of TFSC based on ZnO/PbSe junctions
The most common parameter to test the TFSC performance is the
previously mentioned power conversion efficiency ( ). This para­
meter can be easily estimated by knowing the incident solar power
P0 and the maximum output power Pm as follows [25]:
Pm I ·V FF ·Voc ·Isc
= = m m = , Our TSFC based on ZnO/PbSe junctions achieved comparable
P0 I0 ·Ac I0 ·Ac
where I0 , Ac , Im and Vm correspond to the incident solar irradiance
(0.1 W/cm2 in our case), the cell active area, the maximum photo­
current and the voltage, respectively. The Ac parameter corresponds
to the cell cross-sectional area, which is perpendicular to the current
flow and can be estimated considering different criteria [26].
Some criteria can considerably underestimate or overestimate Ac ,
consequently affecting the reliability of the value. In our case, we
set Ac 1.06 cm2 considering an effective active area of 0.85 cm ×
1.25 cm. This area was determined by the ZnO/PbSe bilayer dimen­
sions (see inset scheme in Fig. 4(a)). Another popular criterion
considers the work electrodes area to estimate Ac . We could consider
the silver work electrode dimensions (0.5 cm × 0.8 cm 0.43 cm2) for
calculations, but we would overestimate considerably the
Jsc = Isc/ Ac = I (V = 0)/ Ac and values. Thus, the most pessimistic
criterion of considering Ac as the area of the active bilayer compo­
nent was used.
Fig. 4. Record photovoltaic performance registered for our TFSC based on ITO/ZnO/PbSe/Ag structures. The highest value was achieved using the proposed ITO/ZnO/PbSe
( X = 13)/Ag structure. Here, the (a) I (current) – V (voltage) and (b) P (power) – V (voltage) curves are shown. The Jsc and parameters were calculated assuming the bilayer active
area criterion, which determined an Ac 1.06 cm2.
Journal of Alloys and Compounds 871 (2021) 159559
Fig. 4 shows the record photovoltaic performance registered for
the most efficient TFSC based on the ITO/ZnO/PbSe( X = 13)/Ag
structure (sample A). In this case, a maximum output power Pm of
3.2 [mW] over a P0 = 106 mW was achieved. Values for FF , Voc , Jsc and
of 25.8%, 0.51 V, 21.4 mA/cm2 and 3.0% were estimated, respec­
tively. Otherwise, the I V behavior was observed to be slightly
nonlinear. This behavior was well-described considering an ex­
ponential tendency following the typical response expected for
diode-like n-p junctions [25].
Fig. 5 shows the photovoltaic performance test results for the
different TFSC based on ZnO/PbSe junctions. A total of five I V
measurements per sample were carried out. In general, nonlinear
I V behaviors were observed. Minimum values for FF , Voc , Jsc , Pm
and of 25.4%, 0.39 V, 17.9 mA/cm2, 2.0 mW and 1.9% were achieved,
respectively. Average values of 2.6 ± 0.3, 2.4 ± 0.4 and 2.4 ± 0.2
were estimated for cells based on samples A, B and C, respectively. To
practical effects, no considerable difference in the photovoltaic
performance was observed between the different samples. In par­
ticular, our results are comparable to other ones reported by similar
research based on ZnO/PbSe junctions. In Table 1, a comparison
between the most important photovoltaic parameters (FF , Voc , Jsc and
) achieved in our research and others reported in the literature
[9–11] is shown.
(9)
photovoltaic performances and even better (in some cases) than
those reported by combining VPD and APCD methods for the ZnO/
PbSe bilayers deposition [9–11]. In terms of parameters like Jsc , Voc
and our cells reached comparable or sometimes higher values than
those reported by different authors (see Table 1). Moreover, the
obtained FF values were similar to those already reported [9–11].
The FF = (Im ·Vm)/(Isc ·Voc) parameter mainly reflects the potential
photovoltaic performance and quality of the solar cell. In general, the
improvement of this parameter can be difficult because it is con­
siderably affected by the diode junction quality [25]. The diode
quality or ideality factor n can be indirectly tested by considering the
I V Schockley diode equation [27]:
qV
I (V ) = Is e nkT 1 ,
(10)
7
S. Roa, M. Sandoval, M.J.C. Burgos et al. Journal of Alloys and Compounds 871 (2021) 159559

Fig. 5. Photovoltaic performance of the different TFSC based on ZnO/PbSe junctions. In particular, the I – V and P – V curves are shown. The Jsc and parameters were calculated
assuming the bilayer active area criterion, which determined an Ac 1.06 cm2.

Table 1 The solar cells I V curves are a superposition of the diode I V

Different ranges for FF , Voc , Jsc and achieved by different research reported in the curve in the dark (Eq. 10) with the light-generated current IL . Con­
literature [9–11], including also our case. Here max denotes the maximum value
sequently, the diode law becomes [28]:
reported by the respective author.
qV
Reference FF [%] Voc [V] Jsc [mA/cm2] [%] max [%]
I (V ) = Is e nkT 1 IL
This work 25.4–29.2 0.39–0.51 17.9–21.5 1.9–3.0 3.0 (12)
Semonin [10] (not reported) 0.04–0.30 12.5–32.0 0.7–4.5 4.5
Hoye [11] 27.1–32.4 0.28–0.41 15.0–22.0 1.3–2.4 2.4 and for diodes with very high n values becomes:
Leschkies [9] 15.0–30.0 0.10–0.45 1.50–15.7 0.6–1.6 1.6
Is V
I (V ) = IL.
n VT (13)

where q , T and Is are the electron charge, the junction absolute Although the observed I V curves could be reasonably fitted
temperature and the reverse bias saturation current, respectively. using an exponential function (see example in Fig. 4(a)) like that
Here, the thermal voltage VT = kT /q 25.86 mV at 300 K is defined. proposed by Eq. (12) this generally involved n 2. Consequently,
The factor n is 1 for the ideal diode, but it usually varies between 1 these curves were observed to be approaching a linear behavior as
and 2. However, it can be higher than 2. For n V / VT with typical V predicted by Eq. (13). In the particular case of the I V curve shown
values between 0 and 1 V, the Eq. (10) can be expressed approxi­ in Fig. 4(a), the fit determined Is and IL values of 24.0 and 22.7 mA,
mately by a Taylor series as: respectively. This Is value is much higher than the typical range of
10−10–10−8 [A] generally observed for diodes with n between 1 and 2
Is V [28]. Thus, our ZnO/PbSe junctions are far away from presenting the
I (V ) = .
n VT (11) ideal diode behavior. This impacts negatively on the FF magnitude,
which can considerably limit the cell efficiency.
So, junctions with high diode quality factors are expected to High diode quality factors mean that recombination currents are
present pretty linear I V behaviors. flowing not homogeneously in the cell because of high defect

8
S. Roa, M. Sandoval, M.J.C. Burgos et al.
concentration zones at local sites [29]. Important defects in the
diode junction structure can be introduced by interfacial roughness
as well as lattice structure mismatch [25]. In TFSC based on het­
erojunctions, which typically involve lattice structure mismatch,
these effects intensify and affect negatively the electron transport
efficiency and recombination at the interface neighborhood. For this
reason, this kind of TFSC usually present considerably lower FF
concerning cells based on homojunctions like the silicon ones
(FF > 70%) [30]. In our case, a considerable lattice structure mis­
match between the ZnO and PbSe films (as shown by the XRD re­
sults) as well as a considerable interfacial roughness (as shown by
the RBS analysis) due to the ZnO films was observed. Thus, we could
suppose the presence of an important defects concentration at the
ZnO/PbSe interface and low FF as consequence. The experimentally
estimated low FF values (25–30%) supported this hypothesis, being
consequent with the observed high diode quality factors (n 2) and
suggesting the poor quality of the ZnO/PbSe junctions in our TFSC.
In synthesis, results suggested the potential photovoltaic activity
of our TFSC based on ZnO/PbSe junctions. Our research particularly
showed that simple and low-cost APCD methods can be used to
fabricate ZnO/PbSe junctions with photovoltaic performances com­
parable to others reported using both VPD and APCD methods. This
fact represents an interesting advance in the cost-performance re­
lation of TFSC based on ZnO/PbSe junctions.
4. Conclusions
Different TFSC based on aqueous-phase chemically deposited
ZnO/PbSe heterojunctions were successfully synthesized by simple
and low-cost APCD methods. The ZnO/PbSe bilayers growth was
observed to be homogeneous and compact, not affecting the crys­
talline structure of the individual materials. The ZnO and PbSe films
presented a Zn and Se excess concerning the other constituent ele­
ments, suggesting possible n and p-type semiconducting behaviors.
Slight nonlinear and exponential photo-generated I V responses
were generally observed for the TFSC. However, these responses
were far away from the ideal diode behavior. This fact impacted
negatively on the FF magnitude, estimating low values between 25%
and 30%. The most efficient cell registered a minimum of 2.3% and
maximum of 3.0% with a FF = 25.8%, Jsc = 21.4 mA/cm2 and
Voc = 0.51 V. In general, all cells presented , Jsc and Voc values higher
than 1.9%, 17.9 mA/cm2 and 0.39 V, respectively. Results clearly
showed the potential photovoltaic activity of our cells and demon­
strated that this kind of simple and low-cost deposition methods can
be used to fabricate ZnO/PbSe junctions with comparable perfor­
mances to others based on both VPD and APCD methods.
CRediT authorship contribution statement
Simón Roa: Conceptualization, Methodology, Validation, Formal
analysis, Investigation, Writing - original draft, Writing - review &
editing, Visualization, Project administration. Myrna Sandoval:
Resources, Writing - review & editing, Supervision, Project admin­
istration, Funding acquisition. María José Cortés Burgos:
Methodology, Validation, Investigation, Writing - review & editing.
Paulraj Manidurai: Methodology, Resources, Writing - review &
editing. Sergio Suárez: Methodology, Formal analysis, Investigation,
Resources, Writing - review & editing.
Data availability
The datasets generated during and/or analyzed during the cur­
rent study are available from the corresponding author on reason­
able request.
9
Journal of Alloys and Compounds 871 (2021) 159559
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors would like to thank FONDECYT Postdoctoral pro­
gram N 3130370; FONDECYT regular N 1130802 CONICYT/FONDAP/
15110019, Government of Chile for financial support. The authors
also thank to Comisión Nacional de Energía Atómica (CNEA,
Argentina) for supplying Scanning Electron Microscopy and X-Ray
Diffraction facilities in the Materials Characterization Department,
Centro Atómico Bariloche (CAB). Finally, the authors would like to
thank Dr. Renato Saavedra (Physics Department, Universidad de
Concepción, Chile) for supplying the equipment to carry out the IR
spectrophotometry measurements.
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