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Solid State Sciences 11 (2009) 224e232

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Preparation and characterization of transparent conducting ZnS:Al films

P. Prathap a, N. Revathi a, Y.P.V. Subbaiah b, K.T. Ramakrishna Reddy a,*, R.W. Miles c
a
Thin Film Laboratory, Department of Physics, Sri Venkateswara University, Chandragiri Road, Tirupati e 517 502, Andhra Pradesh, India
b
Department of Physics, Yogi Vemana University, Kadapa e 516 003, India
c
School of Engineering and Technology, Northumbria University, Newcastle NEI 8ST, UK
Received 7 February 2008; received in revised form 21 March 2008; accepted 23 April 2008
Available online 1 May 2008

Abstract

Al-doped ZnS films were deposited using close-spaced evaporation of the powders synthesized by chemical precipitation method. The films
were prepared for different Al concentrations in the range 0e10 at.% on glass substrates kept at 300  C. The effect of Al-doping on ZnS
composition, microstructure and optoelectronic properties of as-grown ZnS layers was determined using appropriate techniques. The films
were polycrystalline and showed (111) preferred orientation for all the doping concentrations in spite of an additional phase of Al2S3 observed
at higher dopant levels. The surface morphological studies indicated that the Al incorporation had a considerable effect on the surface roughness
of the films. The optical measurements indicated that the optical energy band gap decreased slightly with the increase of dopant concentration
without affecting the optical transmittance characteristics significantly. The electrical analysis indicated that the resistivity of the layers changed
significantly with the doping concentration in the layers. The change of photoluminescence behaviour of the as-grown ZnS:Al films with dopant
concentration was also studied.
Ó 2008 Published by Elsevier Masson SAS.

PACS: 68.55.J; 81.15.E; 73.61.G; 78.66.F

Keywords: ZnS films; Close-spaced evaporation; Structure; Optical properties

1. Introduction material with suitable dopant. The decrease of resistivity by

ZnS is a potential candidate in optoelectronic field despite its
high resistive nature (107 U cm). Its applications can be further
extended if the layers were low resistive, which leads to
a decrease of series resistance of the fabricated device. For
instance, it can be used as window layer in the fabrication of
thin film solar cells due to its higher optical band gap of
w3.6e3.8 eV, which led to the increase in the blue response
of the cell [1]. Most of the successful reports on solar cells
employ highly toxic CdS layers as a window/buffer. The basic
requirements for the window layers are low electrical resistivity
and high optical transmittance. The resistivity can be decreased
either by the creation of excess metal atoms or by doping the
* Corresponding author. Tel.: þ91 877 2249666x272; fax: þ91 877
2249611.
E-mail address: ktrkreddy@hotmail.com (K.T. Ramakrishna Reddy).
the creation of excess metal atoms may not be durable when
the layers are exposed to different atmospheres. Therefore, an
effective way to improve the electrical conductivity of ZnS films
is to dope the layers by suitable dopants preferably from III
group metals like Al, Ga and In without affecting their optical
transmittance characteristics. This can produce shallow donor
levels leading to an improvement in the conductivity of the
layers. In this direction, very less efforts have been made to
produce low resistive ZnS films. Olsen et al. prepared conducting
Al-doped ZnS films by evaporation and they studied the varia-
tion of optical and electrical properties with dopant concentra-
tion [2]. But they did not clearly mention the dopant
percentage in the layers. Lee et al. prepared In-doped ZnS films
and studied their electrical properties as a function of dopant
concentration [3]. Qi et al. [4] studied the effect of copper and
aluminum doping on the luminescence properties of ZnS films.
Karar [5] studied the effect of Cu/Al and codoping of Cl1 and

1293-2558/$ - see front matter Ó 2008 Published by Elsevier Masson SAS.

doi:10.1016/j.solidstatesciences.2008.04.020
 P. Prathap et al. / Solid State Sciences 11 (2009) 224e232
(NO3)1 on the luminescence properties of ZnS crystals. Apart
from the microcrystalline films, nanocrystalline films can offer
distinct advantages like effective optical absorption, lower
recombination losses and pave a way for the fabrication of low
dimensional device structures. [6].
In view of the potentiality and versatility of ZnS compared
to other wide band gap semiconductors, we have adopted an
inexpensive chemical method to prepare Al-doped ZnS
powders. This method is a promising way to produce low
resistive films over a large area due to the uniform distribution
of dopant atoms in ZnS matrix rather than forming concentra-
tion gradient with a lower lattice distortion. ZnS:Al powders
thus synthesized were used to grow the layers by close-spaced
evaporation followed by the characterization of the films using
different techniques. The results obtained in the evaluation
of the physical behaviour of the as-grown ZnS:Al films are
reported and discussed.
2. Experimental
Al-doped ZnS films were prepared on glass substrates by
close-spaced evaporation (CSE) technique with different dop-
ant concentrations that vary in the range 0e10 at.%. ZnS:Al
powders required for evaporation were synthesized in the lab-
oratory by chemical precipitation method. In the preparation
process, we did not use chloride-based precursors in order to
avoid the formation of ZnCl2 complexes in the precipitate,
which degrade the crystalline quality and electrical character-
istics of the grown films. The films were grown under the
optimized deposition conditions achieved in our earlier study
to deposit undoped ZnS layers [7]. The substrate temperature
was maintained at 300  C with the substrate fixed at a distance
of w5 cm from the source. The rate of deposition and film
thickness were kept as 30 Å/s and 300 nm, respectively. The
experimental arrangement of CSE technique was reported
elsewhere [8]. ZnS:Al powder in the form of a pellet was
placed in a molybdenum boat and covered with quartz wool
and a perforated molybdenum sheet to avoid bumping of the
material during evaporation. The system was then pumped
Fig. 1. (a) XRD and (b) EDAX spectra of the ZnS:Al powder.
225
down to a base pressure of 5  106 mbar. The substrates
were sputter cleaned in glow discharge prior to evaporation
in order to remove any impurities present on the substrates.
The vacuum system was again pumped down to a pressure
of 5  106 mbar. The rate of deposition and thickness of
the experimental films were monitored using the quartz crystal
thickness monitor placed just below the substrate holder. The
deposition process and film thickness were controlled by
a shutter placed between the source and substrate. The struc-
tural and morphological studies were carried out using Siefert
X-ray diffractometer and Vecco atomic force microscope,
respectively. The elemental composition of the layers was
studied using VG Microtech ESCA2000 X-ray photoelectron
spectrometer. The spectral transmittance of the films was
recorded as a function of wavelength that varied in the range
300e1500 nm using Hitachi UVeVISeNIR spectrophotome-
ter. The photoluminescence properties were studied using
YVON fluorescence spectrophotometer. The electrical resis-
tivity of the layers was measured using the two-probe method.
Silver was used as electrodes for measuring the resistivity of
the layers. The temperature dependence of electrical conduc-
tivity of the ZnS films was studied in the range 150e450 K.
3. Results and discussion
All the Al-doped ZnS powders synthesized using chemical
precipitation method showed the (111) plane as the dominant
orientation corresponding to the cubic structure of ZnS. The
other peaks observed at 47.61 and 56.37 were attributed to
the (220) and (311) orientations of cubic ZnS. The evaluated
crystallite size and lattice constant of the powder were found
to be w4.8 nm and 4.774 Å, respectively. Fig. 1(a) and (b)
shows the typical X-ray diffractogram and EDAX spectrum
of ZnS powder with an ‘Al’ concentration of 6 at.%, respec-
tively. The elemental composition was found to be Zn ¼
44.75 at.%, S ¼ 49.12 at.% and Al ¼ 6.13 at.%. The powder
samples prepared for different Al-dopant concentrations
were pelletized and evaporated on to glass substrates in order
to prepare Al-doped ZnS films at predetermined conditions.
226 P. Prathap et al. / Solid State Sciences 11 (2009) 224e232
The visual observation of as-grown layers was pinhole free,
uniform and pale yellow in colour. The as-deposited films
were smooth and transparent. They had a distinct advantage
that the adhesion of Al-doped film to the substrate was better
when compared to the undoped films as well as those depos-
ited by the direct evaporation of ZnS powder as was tested
by the Scotch tape method. The thickness of the layers was
approximately 0.3 mm.
3.1. Compositional analysis
X-ray photoelectron spectroscopy (XPS) measurements
were performed to know the dopant incorporation, chemical
composition and state of the elements present in the layers.
The XPS scans were recorded before as well as after the
Arþ bombardment and no changes were observed in the
binding energies and peak shapes due to the Arþ bombard-
ment. Fig. 2 shows the typical XPS spectrum of ZnS layers
grown at a dopant concentration of 6 at.%, recorded in the
range 0e1200 eV. The XPS spectrum exhibited the binding
energies corresponding to Zn 2p3/2, Zn 2p1/2 and S 2p3/2 at
1022 eV, 1046 eV and 162.5 eV, respectively. The observed
binding energies are in good agreement with the reported
data [9]. It has been observed that in the case of Al 2p3/2
centered at 74.02 eV, which originates from Al3þ rather than
metallic Al (72.8 eV), the Al atoms dissolved in ZnS matrix
substituted Zn sites successfully. No other compounds related
to sulfates or organic compounds were observed. In order to
verify the homogeneity of Al content in the layers, one of
the optimized films prepared for an Al concentration of
6 at.% had been etched using Ar and the XPS signal was
analyzed for successive etching times, which showed no
significant change in the XPS signal strength as a function
of etching time. This confirms the uniformity of dopant
concentration across the layer thickness. There was a small
peak in the XPS spectrum at 284.96 eV, which is an indication
of carbon inclusion in the films as the evaporant was synthe-
sized from the organic precursors. The binding energies of
the constituent elements shifted slightly towards lower
Fig. 2. XPS spectrum of ZnS films deposited for an Al-doping concentration of
6 at.%.
energies and peak shapes of core levels remained unchanged
after doping. This may be due to the formation of lattice
distortion caused by Al-doping.
3.2. Structural analysis
The crystallographic studies made using X-ray diffraction
analysis clearly indicated the effect of doping concentration
on the crystalline quality of the grown layers. The X-ray
diffraction spectra of ZnS:Al films for different Al-doping
concentrations in the range 0e10 at.% are shown in Fig. 3.
The comparison of XRD patterns of as-grown undoped and
Al-doped films did not show the essential difference in the
growth orientations and other phases of films in the investi-
gated doping concentration range 0e6 at.%. The (111),
(220) and (311) reflections observed in the XRD spectra of
the films grown in the entire Al-doping concentration corre-
spond to the cubic structure of ZnS. El Hichou et al. [10]
reported cubic and a combination of cubic and hexagonal
phases, respectively, for Al- and Sn-doped ZnS films grown
by spray pyrolysis technique. In the present study, the
as-grown films showed purely cubic structure for all the
dopant concentrations. Moreover, it is interesting to note that
the crystallinity of the films was not seriously affected by
the incorporation of Al in ZnS lattice where the intensity
of the (111) peak increased with the increase of dopant con-
centration to 6 at.% while other orientations such as (220)
and (311) could not be developed significantly. Above this
critical value of dopant percentage, a small indication of
Al2S3 phase could be observed that was confirmed by the
origin of other reflections like (116), (300) and (119) that cor-
respond to Al2S3 phase along with the poor crystallinity. This
indicated the phase segregation at higher dopant concentra-
tion. The initial increase of crystallinity with doping concen-
tration might be due to the incorporation of Al atoms in the
Zn vacancies present in the samples. There were reports in
the literature that the crystallinity of the host material could
not be disturbed noticeably by the incorporation of foreign
dopant atoms upto certain-doping level [11]. Similar increase
of crystallinity with dopant concentration was also reported by
Machado et al. [12] for In-doped ZnO films prepared by elec-
trodeposition. This analysis shows that the presence of alumi-
num helps to improve the crystallinity of ZnS films.
When a material is doped with a suitable dopant, generally at
lower dopant concentrations, new X-ray diffraction peaks may
not appear, instead a gradual shift in the angular positions of
the XRD peaks, corresponding to the host material are observed.
This shift in the diffraction angle is expected because of the
changes that occur in the lattice parameters of the host lattice
on the incorporation of dopant atoms. The position of (111)
peak gradually shifted to higher diffraction angles with the
increase of Al-doping content in the layers. However, the
(111) peak of Al-doped ZnS film shifted back to lower diffrac-
tion angle at higher doping levels, above 6 at.%. This suggests
that Al-doping might have caused some lattice disorder in ZnS
films although the cubic structure was maintained. The variation
of lattice constant ‘a’ as a function of aluminum concentration is
 P. Prathap et al. / Solid State Sciences 11 (2009) 224e232 227

Fig. 3. XRD spectra of Al-doped ZnS films deposited for different dopant levels.

shown in Fig. 4. The lattice constant was found to be 5.416 Å for
undoped ZnS films, which decreased to 5.383 Å for an Al-
doping concentration of 6 at.%. As the radius of Al3þ (0.54 Å)
is lower than that of Zn2þ (0.74 Å) the substitution of Al3þ in
Zn2þ lattice sites could decrease the lattice parameter. However,
the lattice constant increased with further increase of doping
level above 6 at.%, which could be due to the decrease of
number of substitutional Al3þ ions. The Al atoms may be out
diffused from Zn2þ sites at higher dopant concentrations
(>6 at.%), resulting in the interstitial incorporation of Al3þ in
the ZnS crystal lattice. This analysis shows that the solubility
limit of Al in ZnS might be as high as 6 at.%.
The change of strain in the as-grown films as a function of
Al-doping concentration in ZnS layers, as shown in Fig. 5, was
evaluated using the relation [13]
a  a0
3¼  100 ð1Þ
a0
where ‘a’ is the lattice constant of ZnS films and a0 is the
unstrained bulk lattice parameter. The undoped films showed
tensile strain that changed to compressive strain with the
increase of Al-doping density upto 6 at.%. In general, dopant
atoms can occupy substitutional or interstitial positions in the
228 P. Prathap et al. / Solid State Sciences 11 (2009) 224e232
Fig. 4. Change of lattice constant with Al-doping density.
crystal lattice. The increase of compressive strain with the
increase of doping levels might be due to the substitutional incor-
poration of dopant atoms whereas the increase of lattice constant
at higher Al-doping levels (>6 at.%) might be due to the intersti-
tial occupation of Al atoms. The lattice strain present in the
as-grown films might be caused by several factors such as
stoichiometric deviations, difference in the thermal expansion
coefficients of the grown film and the substrate, etc. However,
we thought that strain induced by doping might be dominant in
the present case as all other deposition parameters were kept
constant.
The mean crystallite size, D, of the layers was calculated
using Scherrer’s equation [14]. The crystallite size initially
increased from 42 nm to 56 nm in the dopant concentration
range, 0e6 at.% and decreased to 31 nm with further increase
of the dopant concentration to 10 at.%. This might be due to
the limited solubility of the dopant atoms in the host lattice.
This implies that Al had a considerable effect on the
Fig. 5. Variation of lattice strain with Al-doping concentration.
nucleation and coalescence phases of film growth. Goyal
et al. [15] reported similar observations for indium doped
zinc oxide films and explained the decrease of grain size at
higher In-doping levels in terms of interstitial inclusion of
dopant atoms in ZnO lattice, which results in poor crystallinity
of the films. In polycrystalline films, the texture coefficient
gives a measure of the preferred orientation compared to
a randomly oriented sample. The value of Ci with dopant
concentration was evaluated from the relation [4,13]
ðIi =Ioi Þ
Texture coefficient; Ci ¼ PN
ð1=NÞ i¼1 ðIi =Ioi Þ
where Ii is the intensity of a generic peak in the spectrum, Ioi is
the intensity of a generic peak for a completely random sample
(JCPDS) and N is the number of reflections considered in the
analysis. The variation of crystallite size and texture coeffi-
cient (Ci) with Al-doping concentration is shown in Fig. 6.
The value of Ci is peaked at the dopant concentration of
6 at.%, which shows better crystallinity of the grown samples.
3.3. Morphological analysis
Fig. 7 shows the AFM images of the films grown for three
typical Al-doping densities of 0 at.%, 6 at.% and 10 at.%. The
photographs indicated that the films were smooth and contin-
uous without any pinholes/cracks. The surface morphology of
the Al-doped samples is found to be similar to that of undoped
one. The surface of the layer is covered with equal sized grains
that are uniformly distributed. The grains on the film surface
were more compact and have dense structure. It was also
found that there were variations in the grain size with the
dopant concentration. The grain size increases with the
increase of Al concentration followed upto 6 at.% by
a decrease at higher dopant concentration although the films
were deposited using the same deposition conditions. The
grain size of the films had a maximum at an Al-doping
Fig. 6. The variation of crystallite size and texture coefficient with Al-dopant
level.
 P. Prathap et al. / Solid State Sciences 11 (2009) 224e232 229

electron beam evaporation. The grain size evaluated from

AFM measurements closely matched with the value
calculated from the XRD data. The evaluated average surface
roughness for the films was nearly constant, w1.02 nm upto
Al concentration of 6 at.% and its value increased to
1.57 nm in spite of the decrease of grain size beyond this
doping value.

3.4. Optical studies

Fig. 8 shows the optical transmittance spectrum of ZnS:Al

films with Al-doping percentage. Doping of ZnS films with
‘Al’ shows significant changes in the transmittance character-
istics in the visible region. The average transmittance of pure
ZnS films in the visible region is about 85% whereas ZnS films
doped with Al concentration of 6 at.% showed a transmittance
of 91% that decreased to 65% with further increase of alumi-
num doping level to 10 at.%. The increase of optical transmit-
tance could be due to the better crystallinity and grain size
whereas the decrease of transmittance at higher Al-doping
concentrations (>6 at.%) could be attributed to the lower grain
size, formation of additional phases and higher defect density
that resulted in poor crystallinity of the layers [17]. Moreover,
the sharpness of the absorption edge increased with doping
concentration up to 6 at.% and decreased thereafter. This
shows that the structural disorder seems to be increased at
higher Al-doping concentrations (>6 at.%), which is also
supported by the structural analysis of the layers in the present
study. The optical band gap was determined from the plots of
(ahn)2 vs photon energy, hn by extrapolating the linear region
of the plot onto the energy axis. All the films grown for differ-
ent Al concentrations showed the direct band gap nature and
the evaluated energy band gap with dopant concentration is
shown in Table 1. It varied from 3.79 eV to 3.72 eV when
the doping concentration varied from 0 at.% to 6 at.%.

Fig. 7. AFM pictures of Al-doped ZnS films grown with different Al-doping
densities.

concentration of 6 at.% and decreased beyond this dopant

level. The variation of grain size with doping concentration
implies that there might be some important effect of Al on
the nucleation and coalescence of islands during the process
of film growth. Megahid et al. [16] observed a similar behav-
iour of grain size variation in In-doped CdS films deposited by Fig. 8. Optical transmittance vs wavelength spectra of ZnS:Al films.
230 P. Prathap et al. / Solid State Sciences 11 (2009) 224e232
Table 1
The variation of energy band gap and activation energy with Al-doping
concentration
Al-doping concentration Energy band gap Activation energy (meV)
(at.%) (eV) 150e310 K 310e450 K
0 3.79 21 240
2 3.79 19 209
4 3.75 15 157
6 3.72 11 113
8 3.65 14 138
10 3.54 19 159
According to Pintle et al. [18], the doping of thin films is
effective when the maximum variation of band gap is lower
than 2%. In the present study also, the variation in band gap
with Al-doping is <2% and hence it could be inferred that
the effective doping of Al occurred in ZnS upto 6 at.%.
Generally it is observed that the energy band gap decreases
linearly by doping materials, which is due to the formation of
shallow levels or impurity levels in the band gap region.
Hankare et al. [19] reported a similar variation of band gap
for Pb-doped CdSe films with the dopant concentration. In
this study, the effect of doping on the energy band gap is
marginal upto the dopant concentration of 6 at.%. This
marginal variation of band gap could be explained on the basis
of the fact that the structural defects such as voids and
dangling bonds, which caused the generation of undesirable
localized states in the band gap could be decreased with the
introduction of Al into the ZnS lattice and hence the decrease
of structural disorder that reduces band tailing into the band
gap region [20]. Therefore, the linear decrease of band gap
with the dopant concentration could be compensated by
improvement in the crystalline quality of the layers which
was also supported by the XRD analysis.
3.5. Photoluminescence studies
Fig. 9 shows the room temperature photoluminescence
spectra of Al-doped ZnS layers when excited with the radiation
of wavelength 325 nm. The spectra clearly indicated the effect
of Al incorporation on the photoluminescence characteristics of
ZnS films. The PL spectra of Al-doped layers are much different
from that of undoped ZnS layers and the luminescence intensity
increased with the increase of Al concentration although the
change in the peak position is marginal. The de-convolution of
pure ZnS films gives two peaks at 391 nm and 436 nm. The
luminescence peak located around 391 nm is associated with
the zinc vacancies [21] while the other emission at 436 nm is
associated with zinc interstitials [22]. With the incorporation
of Al into ZnS structure, an additional peak could also be
observed at 470 nm and its intensity increased with the
increase of dopant concentration upto 6 at.%. The observed
luminescence at 470 nm could be ascribed to the self-activated
luminescence that resulted from the donoreacceptor pair
(DAP) transition [23]. The doped Al impurities can form both
the isolated Al donors as well as compensated acceptors, the
density of which depends on the level of the dopant. The donor
Fig. 9. Photoluminescence spectra of ZnS:Al films.
states could be produced by isolated Al donors whereas the ac-
ceptor states could be generated in the form of Zn vacancyeAl
complex, (VZnZnAl). Therefore, the luminescence and electron
transport properties are largely controlled by the compensation
of Al donors. The density of these states increased with the
increase of Al-doping level, which increases the probability of
recombination of DAP. This led to an enhanced luminescence
intensity at higher doping densities (w6 at.%). The decrease
of luminescence intensity at larger doping levels (>6 at.%)
could be due to the formation of Al donor complex that induces
the structural disorder caused by the increase of non-radiative
recombination. Similar decrease of luminescence intensity at
higher doping level was reported by Oh et al. for Al-doped
ZnSe films deposited by molecular beam epitaxy [24]. A broad
luminescence spectrum with low intensity was observed for the
films deposited at a dopant concentration of 10 at.%. This
analysis shows that the compensation of Al donors is dominant
at higher doping levels.
3.6. Electrical studies
The ZnS films in their non-stoichiometric form are known
to have n-type conductivity in which the carriers are generated
from interstitial zinc or sulfur vacancies. The electrical resis-
tivity of ZnS films as a function of Al-dopant concentration
is shown in Fig. 10. It could be observed that the resistivity
of the grown films strongly depends on the Al-dopant level
in ZnS films. It decreased from 2.7  105 U cm to 24 U cm
with the increase of Al concentration from 0 at.% to 6 at.%
and again increased to 6.6  103 U cm with further increase
of Al concentration in ZnS layers upto 10 at.%. The present
trend of resistivity can be explained in terms of solubility
limit of dopant atoms in the host lattice. For Al-doping con-
centration lower than 6 at.%, every Al atom that substitutes
Zn atom in ZnS lattice can contribute one extra free carrier
to the conduction band as the valence difference between
 P. Prathap et al. / Solid State Sciences 11 (2009) 224e232
Fig. 10. Change of electrical resistivity of ZnS films with Al-dopant
concentration.
Al3þ and Zn2þ is 1. As the doping level is increased, more Al-
dopant atoms occupy Zn lattice sites that results in more
charge carriers. However, after certain level of doping, the
dopant atoms cannot occupy the zinc sites due to their limited
solubility. Since the radius of Al atom is less than the radius of
Zn atom, excess Al atoms can occupy the interstitial position
in ZnS lattice [25]. Alternatively, it can be precipitated at the
grain boundaries and form Al2S3 phase as observed from the
XRD analysis. This indicated that the maximum solubility of
Al atoms in ZnS lattice could reach approximately 6 at.%.
Hence, the increase of resistivity at higher doping levels might
be due to impurity scattering or grain boundary potential
effects. Alam and Cameron [26] also reported similar results
in Al-doped ZnO films deposited by solegel process. The
formation (AlZnVZn) acceptor complexes that induce the
self-compensation of the shallow donor impurity levels may
be also responsible for the increase of resistivity as reported
by Prokesch et al. [27], which are identified in Al-doped
ZnSe films. The probability of formation of (AlZnVZn) com-
plexes increases with the increase of dopant concentration
[28]. Therefore, the increase of resistivity was observed at
higher dopant concentrations in the present films.
The temperature dependent electrical conductivity was also
studied in the range 150e450 K for all the samples and the
activation energies were evaluated. Fig. 11 shows the Arrhe-
nius plots of ZnS:Al films deposited in the dopant concentra-
tion range 0e10 at.%. It can be observed from these plots that
the variation of ln s with temperature showed two slopes,
where the change occurred around the annealing temperature
of 310 K. The evaluated activation energies in the two regions
are shown in Table 1. It could be observed that the activation
energy decreased with doping concentration upto 6 at.%. The
decrease of activation energy could be due to the decrease of
energy band gap and effective doping of ZnS. Further, the
increase of crystallinity could also contribute to the observed
decrease of activation energy. The activation energy was found
231
Fig. 11. ln s vs T1 plots for ZnS:Al films.
to increase again with further increase of dopant concentration
that could be due to the formation of additional phases, which
caused the increase of the grain boundary potential and poor
crystallinity of the grown layers.
4. Conclusions
Al-doped ZnS films were successfully prepared by close-
spaced evaporation of the powders synthesized by chemical
precipitation method at different Al-doping concentrations.
The chemical composition of the layers analyzed by using
XPS measurements indicated that the dopant was distributed
uniformly across the layer thickness. The layers showed
predominantly (111) orientation corresponding to cubic struc-
ture of ZnS. However, an additional Al2S3 phase was observed
at higher Al-dopant concentrations. The surface morphological
analysis revealed that the dopant atoms played some role in the
modification of surface roughness and the layers prepared at the
dopant concentration of 6 at.% showed an average roughness of
1.02 nm. These layers showed a higher optical transmittance of
91% with an energy band gap of 3.73 eV. The as-grown layers
showed closely separated photoluminescence peaks that
consisted of Zn and S vacancies and their corresponding inter-
stitials and also the Al-dopant. The luminescence intensity also
decreased at higher doping levels, >6 at.%. The layers prepared
at the dopant concentration of 6 at.% showed a lower electrical
resistivity of 24 U cm and the resistivity was found to decrease
beyond this dopant concentration. These layers showed two
different regions in the Arrhenius plots and the layers prepared
at an optimized dopant level showed lower activation energies
of 11 meV and 113 meV in the low and high temperature
regions, respectively.
References
[1] T. Miyawaki, M. Ichimura, Mater. Lett. 61 (2007) 4683.
[2] L.C. Olsen, R.C. Bohara, D.L. Barton, Appl. Phys. Lett. 34 (1979) 528.
232 P. Prathap et al. / Solid State Sciences 11 (2009) 224e232
[3] J.H. Lee, W.C. Song, K.J. Yang, Y.S. Yoo, Thin Solid Films 416 (2002)
416.
[4] L. Qi, X. Gu, M. Grujicic, W.G. Samuels, G.J. Exarhos, Appl. Phys. Lett.
83 (2003) 1136.
[5] N. Karar, Solid State Commun. 142 (2007) 261.
[6] K. Ernst, A. Belaidi, R. Konenkamp, Semicond. Sci. Technol. 18 (2003)
475.
[7] P. Prathap, Y.P. Venkata Subbaiah, K.T. Ramakrishna Reddy, R.W. Miles,
J. Phys. D: Appl. Phys. 40 (2007) 5275.
[8] Y.P.V. Subbaiah, P. Prathap, K.T.R. Reddy, Appl. Surf. Sci. 253 (2006)
2409.
[9] B. Elidrissi, M. Addou, M. Regragui, A. Bougrine, A. Akchouane,
J.C. Bernede, Mater. Chem. Phys. 68 (2001) 175.
[10] A. El Hichou, M. Addou, J.L. Bubendorff, J. Ebothe, B. El Idrissi,
M. Troyon, Semicond. Sci. Technol. 19 (2004) 230.
[11] I.J. Devos, J.O. Fourcade, J.C. Jumas, P. Lavela, Phys. Rev. B 61 (2000)
3110.
[12] G. Machado, D.N. Guerra, D. Leinen, J.R. Ramos-Barrado, R.E. Marotti,
E.A. Dalchiele, Thin Solid Films 490 (2005) 124.
[13] H.C. Ong, A.X.E. Zhu, G.T. Du, Appl. Phys. Lett. 80 (2002)
941.
[14] B.E. Warren, X-ray Diffraction, Dover, New York, 1990, p. 253.
[15] D. Goyal, P. Solanki, B. Marathi, M. Takawake, V.G. Bhide, Jpn. J. Appl.
Phys. 31 (1992) 361.
[16] N.M. Megahid, M.M. Wakkad, E.K.H. Shokr, N.M. Abass, Physica B
353 (2004) 150.
[17] A. Larena, F. Millan, G. Perez, G. Pinto, Appl. Surf. Sci. 187 (2002) 339.
[18] J.A.D. Pintle, R.L. Morales, M.R.P. Merino, J.A.R. Marquez,
O.P. Moreno, O.Z. Angel, J. Appl. Phys. 101 (2007) 13712.
[19] P.P. Hankare, S.D. Delekar, P.A. Chate, S.D. Sabane, K.M. Garadkar,
V.M. Bhuse, Semicond. Sci. Technol. 20 (2005) 257.
[20] R.A. Smith, Semiconductors, Cambridge University Press, Cambridge,
1964.
[21] H.Y. Lu, S.Y. Chu, S.S. Tan, J. Cryst. Growth 269 (2004) 385.
[22] W.G. Becker, A.J. Bard, J. Phys. Chem. 87 (1983) 4888.
[23] T. Yasuda, K. Hara, H. Kukimoto, J. Cryst. Growth 77 (1986) 485.
[24] D.C. Oh, J.S. Song, J.H. Chang, T. Takai, T. Hanada, M.W. Cho, T. Yao,
Mater. Sci. Semicond. Process. 6 (2003) 567.
[25] D. Cossement, J.M. Streydio, J. Cryst. Growth 72 (1985) 57.
[26] M.J. Alam, D.C. Cameron, J. Vac. Sci. Technol., A 19 (2001) 1642.
[27] M. Prokesch, K. Irmascher, J. Gebauer, R. Krause-Rehberg, J. Cryst.
Growth 214e215 (2000) 988.
[28] G.N. Ivanova, D.D. Negeoglo, N.D. Negeoglo, V.P. Sirkeli,
I.M. Tiginyanu, V.V. Ursaki, J. Appl. Phys. 101 (2007) 63543.