Journal of Materials Science: Materials in Electronics (2019) 30:7600–7605

https://doi.org/10.1007/s10854-019-01075-9

Synthesis of PbS:Mo(3%) thin film and investigation of its properties

Ömer Şahin1 · Arzu Ekinci2 · Sabit Horoz3

Received: 17 December 2018 / Accepted: 5 March 2019 / Published online: 11 March 2019
© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
Pure PbS and PbS:Mo(3%) thin films were synthesized on glass substrates at room temperature using the chemical bath
deposition (CBD) method. The main purpose of this study is to examine the effect of the Mo additive metal on the crystal-
lite size, optical energy band gap and photovoltaic properties of the PbS semiconductor thin film. Although the structure
of PbS:Mo(3%) thin film was the same as the pure PbS, the crystallite size of PbS:Mo(3%) thin film (24.12 nm) was found
to be lower than that of pure PbS (25.97 nm). The band gap values of PbS and PbS:Mo(3%) thin films were obtained as
1.89 eV and 1.91 eV, respectively. The possible reason for the increase in the energy band gap of PbS:Mo(3%) thin film is
the incorporation of ­Mo6+ ions into the PbS lattice. Photovoltaic properties of PbS and PbS:Mo(3%) thin films synthesized
on ­Zn2SnO4 coated on FTO conductive glasses via CBD technique were investigated using the IPCE and J–V measurements.
The IPCE (%) values obtained at 400 nm for the pure PbS and PbS:Mo(3%) thin films were 35% and 41%, respectively. The
power conversion efficiency (η) values were obtained as 2.02% and 2.11% for pure PbS and PbS:Mo(3%) thin films, respec-
tively. Thus, it was observed that the doped metal has significantly improved the photovoltaic properties of PbS thin films.

1 Introduction
Lead sulfide (PbS) is one of the IV–VI semiconductor
compounds with a narrow energy band gap of 0.4 eV. Such
materials are frequently used in sensor applications [1, 2].
Since PbS has a large exciton Bohr radius, a strong quan-
tum confinement effect occurs when it is synthesized in the
nanoscale. Thus, the energy band gap of the nanoparticles
can be controlled by particle size [3–5].
Recently, PbS thin films in the nanosized scale have
attracted great attention in different technological appli-
cations such as sensors [6], photoresistance [7], solar cell
[8] and diode laser [9]. Therefore, It has been made pos-
sible to prepare PbS thin films using different synthesis
techniques such as spray pyrolysis [10], electrodeposition
[11], chemical bath deposition (CBD) [12], successive ionic
layer adsorption and reaction (SILAR) [13] and microwave
* Sabit Horoz
sabithoroz@siirt.edu.tr
1
Department of Chemical Engineering, Faculty
of Engineering, Siirt University, 56100 Siirt, Turkey
2
Department of Occupational Health and Safety, Siirt School
of Health, Siirt University, 56100 Siirt, Turkey
3
Department of Electrical and Electronics Engineering,
Faculty of Engineering, Siirt University, 56100 Siirt, Turkey
heating [14]. In different previous studies [15, 16], PbS thin
films were synthesized by CBD method, one of the chemi-
cal techniques. The reasons for using this method have been
listed as low cost, short time synthesis and no need for inten-
sive laboratory conditions.
One of the effective methods used to improve the opti-
cal properties of thin films is doping [17]. The band gaps
and crystalline sizes of thin films can be tuned by doped
metals. Owing to quantum size effect, the band gaps of
thin films increase as the sizes of crystalline decrease when
they are doped with metal ions. They are different studies
reported on the optical properties of metal doped PbS thin
films. Kumar et al. [18] investigated the optical properties of
Sb-doped PbS thin films synthesized via the CBD method.
They observed that the band gap of Sb-doped PbS thin films
decreased with increasing Sb-doping concentration. They
also reported that the amount of Sb-doping concentration
affected the crystallite size of Sb-doped PbS thin films. Rav-
ishankar et al. [19] made a study on the structural, optical
and magnetic properties of Fe-doped PbS thin films prepared
via spray technique using perfume atomizer. They mentioned
that the Fe-dopant plays an important role to change optical
band gap and crystallite size of Fe-doped PbS thin films. In
contrast to work done by Kumar et al. [18], they observed
that as the particle size decreased, the energy band gap of
the Fe-doped PbS thin films increased. Sr-doped PbS thin

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films synthesized via the CBD method were characterized
by Yucel et al. [20]. They mentioned that the band gap value
of Sr-doped PbS thin films increased from 1.73 to 2.19 eV as
Sr doping concentration increased from 0 to 5%. From the
above literature, it is seen that there is still controversy the
band gap properties of metal-doped PbS thin films.
In our present experimental study, we report the synthesis
and characterization of pure and PbS:Mo(3%) thin films in
the nanosized by the CBD method for the first time. The
influences of Mo dopant on structural, optical and photovol-
taic properties of PbS:Mo(3%) thin films have been inves-
tigated and the obtained experimental results have been
discussed.
1.1 Experimental part and characterization
The materials required to synthesize PbS and PbS:Mo(3%)
thin films on the glass substrates using CBD method at
room temperature are lead nitrate (Pb(NO3)2), thioaceta-
mide ­( C 2 H 5 NS), ammonium molybdate tetrahydrate
((NH4)6Mo7O24·4H2O), sodium hydroxide (NaOH) and
triethanolamine (TEA) ­(C6H15NO3), respectively. 0.1 M
Pb(NO 3)2, 0.1  M ­C2H5NS, 0.5  M NaOH and a certain
amount of TEA were mixed in an 80 mL beaker at room
temperature. The stirring process was continued until a
homogeneous solution was obtained. Then a glass substrate
was immersed in the solution in a vertical position. The sub-
strate was left in the PbS solution for approximately 3 h,
then removed, washed several times with distilled water and
dried in air.
To synthesize PbS:Mo(3%) thin film on a glass substrate
using the same method, 0.003 M ((NH4)6Mo7O24·4H2O)
was added to the above-mentioned solution, respectively
and then all the steps were repeated.
X-ray diffraction (XRD) in a Rigaku X-ray diffractometer
with Cu Kα (λ = 154.059 pm) radiation was used to charac-
terize the structural properties of thin films. UV–Vis absorp-
tion spectra were recorded using a Perkin-Elmer Lambda 2
spectrometer. Energy dispersive X-ray (EDX) (JEOL JSM
5800) was used to study the elemental analysis of thin films.
Incident photon-to-current efficiency (IPCE) measure-
ments were applied to investigate photovoltaic properties
of pure PbS and PbS:Mo(3%) thin films. To carry out IPCE
measurements, pure PbS and PbS:Mo(3%) thin films were
synthesized on Z ­ n2SnO4 coated on FTO conductive glass
substrates instead of glass substrates via the CBD method.
PCE-S20 with a monochromatic light source consisting of a
150 W Xe lamp and a monochromator were used to perform
the IPCE measurements.
2 Results and discussions
XRD patterns for pure PbS and PbS:Mo(3%) thin films syn-
thesized via the CBD technique are indicated in Fig. 1.
The observed five peaks correspond to (111), (200),
(220), (311) and (222) crystalline planes, respectively. The
XRD patterns confirm that the both thin films are the face
centered cubic structure. The result is consistent with a
standard card (JCPDS No. 05-0592). Moreover, the recorded
reflection are free from the impurity planes. The peak posi-
tions of planes of PbS thin film shifted towards the low
Bragg’s angle side when PbS film was doped with Mo metal
ions. The obtained observation indicates that the crystallo-
graphic positions of ­Pb2+ ions have been occupied by M ­ o6+
ions in PbS lattice. This situation clearly shows that ­Mo6+
ions are well-dissolved in the PbS lattice, as the ionic radius
of ­Mo6+ (0.062 nm) is less than that of ­Pb2+ (0.098 nm).
This confirms the PbS:Mo(3%) film forms when ­Mo6+
(0.062  nm) occupies the P ­ b 2+ (0.098  nm) sites in the
PbS lattice since the lattice would undergo a contraction
owing to the smaller ionic radii of ­Mo6+ (0.062 nm). The
Debye–Scherer relation [21] given in the Eq. (1) was used
to calculate the average crystallite size (D) of pure PbS and
PbS:Mo(3%) thin films synthesized via the CBD technique.
The crystallite size of pure PbS and PbS:Mo(3%) thin films
was found as 25.97 nm and 24.12 nm, respectively.
D = 0.9𝜆/(𝛽 cos 𝜃) (1)
where D is the mean crystalline size of the nanoparticles, 𝜆
is the wavelength of X-ray, 𝛽 is the broadening measured as
the full width at half maximum (FWHM) in radians, and 𝜃
is Bragg diffraction angle.
The main purpose of the studies on optical measurements
is to examine the band structure of thin films synthesized
Fig. 1  XRD patterns of pure PbS and PbS:Mo(3%) thin films synthe-
sized via the CBD technique
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Fig. 2  Optical absorption spectra of pure PbS and PbS:Mo(3%) thin
films synthesized via the CBD technique
in nanoscale. Thus, it can be predicted how much energy
band gap they have. The absorption spectrum for PbS and
PbS:Mo(3%) thin films synthesized via the CBD technique
are indicated in Fig. 2 as a result of optical measurements
using UV–Vis absorption spectroscopy.
There are two important observations should be noted.
(1) The absorption edges both samples shift to lower wave-
lengths (blue-shift) with respect to the bulk PbS. (2) The
absorption edge of PbS:Mo(3%) thin film is also blue-shifted
compared to PbS thin film. The probable cause of observing
this is the decrease in the crystallite size of PbS thin film in
the presence of Mo additive ions.
Tauc’s relation [22] is given in Eq. (2) was used to deter-
mine band gap of pure PbS and PbS:Mo(3%) thin films.
)n
(2)
(
αhυ = C hυ − Eg
where α is the absorption coefficient, n = 1/2 or 2 for direct
or indirect allowed transition, respectively, C is the char-
acteristic parameter for respective transitions, hυ is photon
energy and ­Eg is energy band gap. Figure 3 demonstrates
(αhυ)2 versus hυ for PbS and PbS:Mo(3%) thin films syn-
thesized via the CBD technique.
The band gap values of PbS and PbS:Mo(3%) thin films
were obtained as 1.89 eV and 1.91 eV, respectively. The
reason of increment in the band gap of PbS:Mo(3%) thin
film could be due to the quantum confinement effect. This
effect occurs if crystallite size of the thin film is equal to
or less than its exciton radius. Another meaning of the
quantum confinement effect is that as the crystallite size
of thin film decreases, the energy band gap value of that
thin film increases. However, since the crystallite size of
PbS (25.97 nm) and PbS:Mo(3%) (24.12 nm) thin films are
larger than the excitonic Bohr radius of PbS (18 nm) it is
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Journal of Materials Science: Materials in Electronics (2019) 30:7600–7605
Fig. 3  Plots of (αhν)2 versus hν of pure PbS and PbS:Mo(3%) thin
films synthesized via the CBD technique
not possible to mention the quantum confinement effect in
the present study. Another possible reason for the increase
in energy band gap of PbS:Mo(3%) thin film is the incor-
poration of ­M o 6+ ions into the PbS lattice. Thus, since
positions of ­Pb2+ ions have been occupied by ­Mo6+ ions
in PbS lattice, the band gap of PbS:Mo(3%) have become
wider than that of PbS thin film.
Photovoltaic properties of PbS and PbS:Mo(3%) thin
films synthesized on ­Z n 2SnO 4 coated on FTO conduc-
tive glasses via CBD technique were investigated using
the IPCE measurements. Figure 4 demonstrates the IPCE
spectra for PbS and PbS:Mo(3%) thin films.
It was observed that PbS:Mo(3%) thin film synthesized
on ­Zn2SnO4 coated on FTO conductive glass had higher
IPCE (%) value compared to IPCE (%) value of pure
PbS thin film. The IPCE (%) values obtained at 400 nm
for the pure PbS and PbS:Mo(3%) thin films were 35%
and 41%, respectively. This result shows that Mo addi-
tive metal plays an important role in the development of
photovoltaic properties of PbS thin films. The possible
reasons why PbS:Mo(3%) thin film has a higher IPCE (%)
value than the pure PbS thin film can be listed as follows;
(1) the penetration of ­Mo6+ (0.062 nm) ions with a lower
ionic radius compared to ­Pb2+ (0.098 nm) ions into the
PbS lattice increases the number of electrons stimulated
to the external circuit. (2) The spectral response range of
PbS:Mo(3%) thin film is wider than that of pure PbS thin
film. This phenomenon, which can provide electrons in the
long wavelength region of the spectrum of PbS:Mo(3%)
thin film, is due to the occurrence of mid-range condi-
tions between the transmission band and the valence band
of ­Z n 2SnO 4. Therefore, the IPCE (%) efficiency of the
PbS:Mo(3%) thin film having a wider spectral response
range is higher than the pure PbS thin film.
Journal of Materials Science: Materials in Electronics (2019) 30:7600–7605 7603

Fig. 4  IPCE spectra of pure

PbS and PbS:Mo(3%) thin films
synthesized on Z
­ n2SnO4 coated
on FTO conductive glasses via
CBD technique

The current density (J) versus voltage (V) plots for pure
PbS and PbS:Mo(3%) thin films synthesized on Z ­ n2SnO4
coated on FTO conductive glasses via CBD technique are
indicated in Fig. 5.
It is important to note that there is a significant improve-
ment in the performance of PbS:Mo(3%) thin film based
solar cell when compared with pure PbS based solar cell.
The power conversion efficiency (η) values were obtained as
2.02% and 2.16% for pure PbS and PbS:Mo(3%) thin films,
respectively. Open circuit voltage ­(VOC), short circuit current
density ­(JSC) and power conversion efficiency (η%) values
for both samples are given in Table 1.

Fig. 5  J–V plots of pure PbS

and PbS:Mo(3%) thin films
synthesized on Z­ n2SnO4 coated
on FTO conductive glasses via
CBD technique

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Table 1  The obtained V­ OC, ­JSC and η% values for pure PbS and
PbS:Mo(3%) thin films synthesized on ­Zn2SnO4 coated on FTO con-
ductive glasses via CBD technique
Sample (thin film) JSC (mA/cm2) VOC (V) η%
PbS 9.22 0.40 2.02
PbS:Mo(3%) 9.63 0.40 2.11
When the data given in the Table 1 are taken into consid-
eration, it is observed that the η (%) value of PbS:Mo(3%)
thin film significantly increased as a result of doping pro-
cess. The possible causes of this increase can be listed as
follows; (1) In IPCE spectra, PbS:Mo(3%) thin film has a
wider spectral response than pure PbS thin film, causing this
sample to has higher ­JSC value. This provides an enhance-
ment in the efficiency of PbS:Mo(3%) thin film based solar
cell. (2) Reduces the recombination of photo-excited carriers
that may occur due to the fact that the PbS:Mo(3%) thin film
has a lower particle size than the pure PbS thin film. This
effect leads to a significant increase in power conversion.
Thus, both IPCE and J–V measurements have been shown
experimentally that PbS:Mo(3%) thin film can be used as a
promising sensitizer in photovoltaic applications.
3 Conclusions
In the present study, pure PbS and PbS:Mo(3%) thin films
in nanoscale were synthesized on glass substrates using the
CBD method at room temperature. Both of the synthesized
thin films were found to have cubic structure as a result of
XRD measurements. The crystallite sizes of pure PbS and
Mo doped PbS thin films using XRD data were calculated
as 25.97 and 24.12 nm, respectively. The effect of Mo-doped
metal on PbS crystallite size was clearly observed. Optical
absorption measurements were performed to examine the
band structures of pure PbS and PbS:Mo(3%) thin films and
the energy band gap values of pure PbS and PbS:Mo(3%)
thin films were determined as 1.89 and 1.91 eV, respectively.
The reason for the increase in the energy band gap is the
incorporation of M­ o6+ ions into the PbS lattice. Photovol-
taic properties of PbS and PbS:Mo(3%) thin films synthe-
sized on Z­ n2SnO4 coated on FTO conductive glasses via
CBD technique were investigated using the IPCE and J–V
measurements. The IPCE (%) values obtained at 400 nm
for the pure PbS and PbS:Mo(3%) thin films were 35% and
41%, respectively. The power conversion efficiency (η) val-
ues were obtained as 2.02% and 2.11% for pure PbS and
PbS:Mo(3%) thin films, respectively. Thus, it was observed
that the doped metal has significantly improved the photo-
voltaic properties of PbS thin films.
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