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Evolution of the energy band structure in chemical-bath-deposited CdS thin films studied by

optical absorption spectroscopy

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2011 Semicond. Sci. Technol. 26 055012

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IOP PUBLISHING SEMICONDUCTOR SCIENCE AND TECHNOLOGY
Semicond. Sci. Technol. 26 (2011) 055012 (5pp) doi:10.1088/0268-1242/26/5/055012

Evolution of the energy band structure in

chemical-bath-deposited CdS thin films
studied by optical absorption spectroscopy
A Aşıkoğlu and M H Yükselici1
Department of Physics, Faculty of Science and Letters, Yıldız Technical University, Davutpaşa cad.,
34210 Esenler, İstanbul, Turkey
E-mail: yukseli@yildiz.edu.tr

Received 19 October 2010, in final form 12 January 2011

Published 16 March 2011
Online at stacks.iop.org/SST/26/055012

Abstract
CdS thin films were grown on glass substrates by chemical bath deposition. Increasing
deposition time from 10 to 200 min at an ultimate bath temperature of 60 ◦ C gives rise to a red
shift in optical absorption edge of ∼1 eV and a decrease in the Urbach tail width from 520 to
370 meV. A semi-empirical model was developed to account for the decrease of band gap
energy with deposition time based on possible lattice contraction at the earlier stages of thin
film growth. The degree of structural disorder related to the Urbach tail width was shown to be
proportional to unharmonic terms in potential energy of atoms vibrating asymmetrically. An
increase in band gap energy with increasing heat-treatment temperature was observed and
explained by a quantized-state effective mass model in the strong confinement limit which
predicts a blue shift in band gap energy of ∼0.5 eV as the grain size decreases from 7.6 to
2.2 nm due to a decrease in sulfur concentration in grains. Combined use of the Arrhenius plot
and quantum size effect yields activation energy of 46 kJ mol−1 for the diffusion of sulfur
during the heat treatment.

1. Introduction
CdS thin film has been the best heterojunction partner for
CdTe which is an ideal absorber for thin-film solar cells
[1–3]. Chemical bath deposition (CBD) is one of the low-
cost and highly-efficient routes for depositing CdS thin films
[4–9]. The optical and structural properties of CBD CdS
thin films have been scrutinized for two decades. Mahanty
et al [10] reported that the band gap energy for as-deposited
films decreases with increasing Cd/S ratio. Ramaiah et al
[11] analyzed XRD results using Scherrer’s relation and
concluded that the grain size decreased with decreased sulfur
concentration to a minimum value of ∼3 nm. Rakhshani and
Azab [12] employed optical absorption spectroscopy and XRD
to study the dependence of film thickness on band gap energy
and the inter-planar spacing. They found that the band gap
energy decreases with increasing film thickness and that the
inter-planar spacing of (0 0 2) planes of a hexagonal structure
1 Author to whom any correspondence should be addressed.
is smaller than that of the bulk value at the initial stages of film
deposition due to tensile strain.
In this work CdS thin films were grown on glass substrates
by CBD. Time evolution of the band gap energy and Urbach tail
width were studied through optical absorption spectroscopy.
We have derived an expression which relates the degree of
structural disorder to the unharmonic terms in vibrational
potential energy of atoms. The effect of heat treatment on
the band gap energy was discussed in terms of out diffusion of
sulfur from grains and quantum confinement effect.
2. Experimental details
2.1. Sample preparation
A bath of pH = 11.6 was prepared from 0.1 M of cadmium
sulfate, 1 M of thiourea, each separately dissolved in 30 ml
of distilled water and 1.25% ammonium hydroxide according
to the procedure reported in [4]. A pair of glass slides was
cleaned in 1.25% HCl for 0.5 h, then washed with acetone
and distilled water and finally dried in an oven. They were

0268-1242/11/055012+05$33.00 1 © 2011 IOP Publishing Ltd Printed in the UK & the USA
Semicond. Sci. Technol. 26 (2011) 055012 A Aşıkoğlu and M H Yükselici

Figure 1. OD plotted against photon energy for chemical Figure 2. Band gap energy (Eg ) plotted against deposition time.
bath-deposited CdS thin films. Deposition times are numbered as The curve is a fit based on a semi-empirical model for the time
follows: 1 → 10, 2 → 16, 3 → 22, 4 → 28, 5 → 34, 6 → 40, 7 → dependence of the band gap energy.
60, 8 → 90, 9 → 150 and 10 → 200 min.

immersed vertically in the reaction bath which was kept under

stirring at 250 rpm and at a temperature increasing from 23 to
60 ◦ C at a rate of ∼2 ◦ C min−1 . It should be noticed that 60 ◦ C
is the ultimate bath temperature which remains fixed once it has
been reached. The aqueous solution and the glass substrates
first turn pale yellow and then light orange within 8–10 min.
The glass slides coated with CdS thin film were washed with
methanol and then with distilled water. A set of ten thin films
on glass substrates with deposition times ranging from 10 to
200 min was set apart and a small area of dimensions 3 ×
3 mm2 with good deposition uniformity was marked on each
sample for optical characterization.

2.2. Experimental results

All the samples were characterized by optical transmission
measurements at room temperature. Optical density (OD)
is plotted against photon energy (hν) in figure 1. As the
deposition time increases, optical absorption increases for all
photon energies, and the asymptotic absorption edge with a tail
structure shifts to lower energies. The straight-line portions of
the OD squared against photon energy curves are extrapolated
to obtain the band gap energies (Eg ) as intercepts with the
∗
OD2 = 0 axis according to the square law: OD2 = (A d)2 (hν–
∗
Eg ), where A is a constant and d is the film thickness [13]. In
figure 2 the band gap energy for each thin film sample is plotted
against deposition time. The curve through the data points is
a fit based on a semi-empirical model for time dependence of
band gap energy discussed in the next section.
The Urbach tail width, i.e. the Urbach energy (Eu ) is
defined by OD = ODo e(hν−Eg)/Eu and calculated from the
slope of least-squares fit to the straight portion of InOD against
Figure 3. Urbach energy (Eu ) on the left vertical axis and the degree
of structural disorder (X) on the right vertical axis plotted against
deposition time.
the hν curve, where ODo is a constant. The Urbach energy
is plotted against the deposition time in figure 3. The right
vertical axis is the unitless structural disorder parameter (X)
which is discussed in the next section. In figures 1–3, the
deposition time represents the duration required for the bath to
reach the ultimate bath temperature of 60 ◦ C plus the duration
at that constant temperature. Only sample 1 was taken out of
bath at 55 ◦ C before reaching the ultimate bath temperature.
However inclusion of data for sample 1 does not alter the

2
Semicond. Sci. Technol. 26 (2011) 055012
Figure 4. Band gap energy plotted against heat-treatment
temperature. The straight line is a linear fit with a slope of 2 ×
10−3 eV ◦ C−1 .
general trend established for other samples deposited at an
ultimate bath temperature of 60 ◦ C.
One thin film sample deposited for 150 min was heat
treated at temperatures ranging from 250 to 400 ◦ C for 3 h.
The band gap energy is plotted against the heat-treatment
temperature T in figure 4. The straight line through the data
points is a linear fit with a slope of 2 × 10−3 eV ◦ C−1 . We
observe a blue shift of optical absorption edge with heat-
treatment temperature. Although there are some reports in
support of our observation in this work for the blue shift of
the band gap energy with heat-treatment temperature [14], we
note that it is a rarely observed phenomenon. Most of the
researchers have reported a red shift in the band gap energy
with heat treatment [7, 15, 16].
3. Discussion
3.1. Time dependence of the band gap energy
It is important to understand the time evolution of the band
gap energy for solar cell applications since the efficiency of a
window layer depends on the band gap energy. We therefore
derive first an expression for the band gap energy of thin film
as a function of the deposition time. The bulk modulus is given
by
P
B=− (1)
V /Vi
where P is the change in pressure, V is the change in
volume and Vi is the initial volume. The rate at which the
band gap energy changes with the volume of a unit cell might
be expressed in terms of the bulk modulus and the rate at which
the band gap energy changes with pressure:
dEg B dEg
=− (2)
dV Vi dP
3
A Aşıkoğlu and M H Yükselici
by integrating over the volume of the unit cell,
 Egfilm 
B dEg Vf <Vi
dEg = − dV (3a)
Egbulk Vi dP Vi
  3 
dEg cf
Egfilm = Egbulk +B 1− , (3b)
dP ci
where we assume that Vi(f ) ≈ ci(f 3
) , initial (final) lattice
constant, and dEg /dP = 28.5 meV GPa−1 for bulk CdS
crystal [17]. We propose that the observed band gap shift in
figure 2 during film growth is due to tensile strain and that the
film under tensile strain responds to the electromagnetic field
as if it is under pressure. We therefore employ crystal’s bulk
modulus and the coefficient for the pressure dependence of the
band gap.
Strain-related modifications in lattice parameters in thin
films of CdS grown by CBD have been studied through XRD
[12, 18, 19]. It has been reported that the inter-planar spacing
of (0 0 2) planes for CdS crystal during the deposition increases
with the film thickness to that of the bulk value [12]. Based
on the experimental result reported in [12], we approximate
the thickness dependence of the inter-planar spacing which
is proportional to the lattice constant cf with a one-minus-
exponential function. Furthermore we assume proportionality
between the film thickness and the deposition time from the
works in [5, 20], and we therefore propose that the lattice
constant also increases with deposition time through one-
minus-exponential function:
cf = ci (1 − b e−λt ) (4)
where b and λ are the fitting parameters. As t → ∞, the lattice
constant approaches to that of the bulk value of cf → cbulk =
0.673 nm for the CdS crystal of a hexagonal structure [21].
We finally obtain an expression for the time dependence of the
band gap energy by inserting equation (4) into equation (3b):
dEg
Egfilm = Egbulk + B [1 − (1 − b e−λt )3 ]. (5)
dP
We fit Egfilm against the deposition time plot in figure 2
with a curve given by equation (5) and calculate best fitting
parameters as λ = 4.1 × 10−4 s−1 and b = 0.25. As the
deposition time gets very large values, the asymptotic band
gap energy of the thin film approaches to that of the bulk
structure. It has been reported that gradually decreasing Cd
concentration in the reaction bath with time demounts tension
at the substrate–layer interface which translates to a decrease
in the band gap energy [22]. The observed decrease in the
band gap energy suggests that the limiting reactant during the
nucleation stage which controls the film growth is cadmium
concentration.
3.2. Urbach energy and structural disorder
Thermal displacement of atoms away from the equilibrium-
state-lattice sites, that is, lattice contraction, at the initial stages
of thin film growth modifies the energies of phonon modes
which interact with excitons. The phonon–exciton interaction
determines the sub-band gap absorption shape. The Urbach
Semicond. Sci. Technol. 26 (2011) 055012 A Aşıkoğlu and M H Yükselici

rule states that the optical absorption at the long-wavelength
tail has an exponential form which depends on the temperature
T and the degree of structural disorder X. According to the
Cody model [23] the Urbach energy Eu is related to the
temperature and disorder by the equation
  
Ep Ep
Eu = X + coth (6)
2σo 2kB T
where Ep of 25 meV is the phonon energy, σ o of 1.19 is
a material-dependent parameter [12] and X is a measure of
structural disorder which is defined as the ratio of the mean
square deviation of atomic position U 2 to the zero-point
uncertainty in the atomic position squared Uo2 :
U 2
X= . (7)
Uo2
We set T to room temperature of 295 K and calculate the
structural disorder parameter X corresponding to each Urbach
energy value according to equation (6) as shown in figure 3
on the right vertical axis. The Urbach energy decreases with
deposition time sharply from 520 to 370 meV and stabilizes at
around 400 meV. The range in which the Urbach energy varies
agrees with previous results at room temperature [20].
The unharmonic terms in the potential energy of the atoms
should be taken into account because of the asymmetry in
the potential around the surface atoms due to the absence of
nearest neighbor on the air–surface interface [24]. We assume
one-dimensional unharmonic potential energy of the form [25]
which states that the structural disorder increases at the
earlier stages of the film deposition due to the unharmonic
vibrations which is represented by the coefficient f . At a fixed
temperature the structural disorder increases linearly with the
strength of unharmonic terms.
3.3. Blue shift in the band gap energy with heat-treatment
temperature
Self-diffusion of an atom across the surface is possible due
to thermal energy fluctuations [24]. Various researchers have
reported that sulfur is volatile so it might have dissociated
from CdS grains throughout diffusion on heat treatment
[10, 14]. On the other hand the grain size decreases with
decreasing sulfur content [11]. Both non-stoichiometry, i.e.
sulfur deficiency, and size decrease might induce band gap
modifications. However, by applying a parameterized tight-
binding density-functional method Joswig et al [26] showed
that the quantum size effect controls band gap modifications
and that the non-metal atoms move outward through a surface
layer of around 0.25–3 nm. The blue shift in energy observed
in figure 4 is presumed to be due to the decreasing grain size
and can be explained by the quantum confinement effect [11].
In the strong confinement regime, the energetic position of the
first exciton peak is given by [27]
 
2 2 2
h̄ x1,0 x1,0
E1,0 (R) = Egbulk + + (11)
2R 2 me mh

PE = Ax 2 − gx 3 − f x 4 (8) where R is the average radius of grains, x1,0 = π is the first

root of the spherical Bessel function and me(h) is the effective
where A, g and f are all positive. The terms of third and
mass of electrons (holes). Equation (11) predicts a grain size
fourth order in the x’s are known as the unharmonic terms.
ranging between 7.6 nm at 250 ◦ C and 2.2 nm at 400 ◦ C.
We calculate the mean square deviation of atomic positions by
We then calculate the activation energy for the out
using the Boltzman distribution function [25] and assuming
diffusion of sulfur by considering the reverse situation in
equation (8) for the potential energy (PE):
which the grain size increases with the in diffusion of sulfur.
+∞ − kPET According to the diffusion-limited growth, for the case of
−∞ dxx 2 e B
U 2
= (9a) quasi-static diffusion around a particle, the average radius
− kPET
∫+∞
−∞ dx e
B
increases as [28]
 
kB T 12(f/A)kB T R 2 = Ro2 + CDt (12)
U 2 = 1+ . (9b)
2A 4A + 3 (f/A) kB T where D is a diffusion coefficient, t is the heat-treatment
We estimate the zero-point vibrational amplitude Uo2 time and C is a constant. We set the initial particle radius
by employing basic physics and literature bulk value of at t = 0 equal to the smallest grain size of Ro = 1.14 nm
2.85 × 10−18 cm2 for UCd 2
|| c at 295 K [21]. We find Uo =
2 as determined by plugging the band gap energy of 4.25 eV
0.65 × 10 −18 2 2
cm . However it should be noticed that the calculated using equation (5) with t = 0 into equation (11).
mean square amplitude of vibration at the surface will have The diffusion coefficient at a constant pressure is correlated
higher values than that of bulk atoms [24]. By assuming with the temperature through an Arrhenius relationship,
4A 3(f/A)kB T in equation (9b) we find the following D = Do e−Q/R T (13)
expression for the structural disorder:
  where Do is a frequency factor, Q is the molar activation energy,
f
X ≈ 1 + 3 2 kB T (10) R is the universal gas constant and T is the heat-treatment
A temperature. Combining equations (11)–(13) yields
2 The vibrational energy at a temperature T is set equal to the thermal
 
2 2
h̄2 x1,0 x1,0
energy kU 2 /2 = kB T /2 to find the stiffness constant of k=14.3 N m−1 . In + − Ro2
The frequency
√ of vibration of ω=8.75×1012 Hz is calculated by using 2(E1,0 − Egbulk ) me mh
ω = k/mCd where mCd is the atomic mass of cadmium. The zero-
Q(kJ) 1000
point vibrational energy is set equal to the vibrational energy at T=0 K: =− + In(CDo t) (14)
ω/2 = kUo2 /2 which yields Uo2 =0.65 × 10−18 cm2 . 8.314 T (K)

4
Semicond. Sci. Technol. 26 (2011) 055012
Figure 5. Natural logarithm on the left-hand side of equation (14)
plotted against 1000/T (T: heat-treatment temperature).
where E1,0 is set equal to Egfilm . In figure 5 the natural logarithm
on the left-hand side of equation (14), i.e. In{ . . . } is plotted
against 1000/T(K). The activation energy for the diffusion of
sulfur is calculated as Q = 46 kJ mol−1 from the slope of the
least-squares straight-line fit to data in figure 5.
We have also calculated the Urbach tail width for heat-
treated samples and observed that the Urbach energy fluctuated
over a wide range between 350 and 650 meV, that is, no general
trend could be established.
4. Conclusions
The asymptotic absorption edge for chemical bath-deposited
CdS thin films decreases ∼1 eV with deposition time according
to a time-dependent function based on a semi-empirical model
which presumes lattice contraction at the earlier stages of
thin film growth. The Urbach energy also decreases with
deposition time sharply from 520 to 370 meV and stabilizes at
around 400 meV. The degree of structural disorder related to
the Urbach energy is proportional to the unharmonic terms in
the potential energy of atoms vibrating asymmetrically. Sulfur
leaves the grains through diffusion with heat treatment at 250–
400 ◦ C so that the grain size decreases from 7.6 to 2.2 nm which
causes a blue shift of ∼0.5 eV in the asymptotic absorption
edge due to the quantum confinement effect. Combined use
of the Arrhenius plot and quantum size effect yields activation
energy of 46 kJ mol−1 for the diffusion of sulfur during the
heat treatment. It should be pointed out that direct (such as
SEM) and indirect (such as XRD) microstructural analyses to
back the hypotheses based on optical studies in the present
A Aşıkoğlu and M H Yükselici
contribution are very useful to assess the relative weight of the
results obtained and conclusions drawn.
Acknowledgments
This work has been supported by Yıldız Technical University
Research Projects Coordination under project no 26-01-01-01.
We thank Türkan Doğan for her assistance while conducting
preliminary research on CBD CdS.
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