Journal of Physics and Chemistry of Solids 73 (2012) 13091313

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Journal of Physics and Chemistry of Solids

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Effect of thickness on the structural, optical and electrical properties

of thermally evaporated PbI2 thin lms
Mohd Shkir a,b,c,n, Haider Abbas b, Siddhartha c, Ziaul Raza Khan c
a
Department of Physics, ARSD College, University of Delhi, New Delhi 110021, India
b
Department of Physics, Manav Rachna College of Engineering, Faridabad, Haryana 121001, India
c
Department of Physics, Jamia Millia Islamia (a central university), New Delhi 110025, India

a r t i c l e i n f o abstract

Article history: This work describes the physical properties of lead iodide (PbI2) thin lms with different thicknesses
Received 16 October 2011 that were deposited on ultrasonically cleaned glass substrates using a thermal evaporation technique at
Received in revised form 5  10-6 torr. The initial material was puried by the zone rening technique under an atmosphere of
15 April 2012
argon gas. XRD analysis of the material demonstrates that the thin lms were preferably oriented along
Accepted 30 April 2012
the (001) direction. The size of the crystallites was calculated from the Scherer relation and found to be
Available online 10 May 2012
in the range of  510 nm, with higher values being observed for increasing lm thicknesses. The
Keywords: optical energy band gaps were evaluated and determined to belong to direct transitions. Because the
A. Semiconductors band gap increased with decreasing lm thickness, a systematic blue shift was observed. The surface
A. Thin lms
morphologies of PbI2 lms exhibited a clear increase in grain size with increasing lm thickness. The
C. Electron microscopy
photoluminescence and dc conductivity of the thin lms are also discussed.
C. X-ray diffraction
D. Optical properties & 2012 Elsevier Ltd. All rights reserved.

1. Introduction these devices depends on the fabrication technique and growth

Currently, thin lms constitute one of the most important
technologies for the development of optoelectronic devices.
Materials prepared from thin lms have potential applications
in computers, drugs and dye-sensitized solar cell devices. Lead
iodide (PbI2) is a semiconducting material with a wide band gap
(Eg  2.3 eV). Due to the high atomic number of its elements
(ZPb 82, ZI 53), PbI2 has potential to be used in ionizing
radiation detectors (X- and g-rays) [13]. Moreover, this material
can detect ionizing radiation at room temperature using the
direct detection method, which is particularly suitable for low
energy X-ray [48].
In recent years, polycrystalline PbI2 thin lms have also been
extensively studied as direct converters in high-energy detectors,
due to their promising semiconductor properties [912]. The
large optical energy band gap of this material is useful from a
technological point of view because it is an essential parameter
for the production of various optoelectronic devices, such as
detectors or converters of digital radiography into mammography
energy region [11,12]. Thin lms of PbI2 can also be used for the
detection of X-ray imaging [13]. The application of lead iodide in
n
Corresponding author at: Department of Physics, Atma Ram Sanatan Dharam
College, University of Delhi, New Delhi 110021, India. Tel.: 91 9911769335;
fax: 91 1124111390.
E-mail addresses: shkirphysics@gmail.com, shkir.mrce@mrei.ac.in (M. Shkir).
process [1418]. The physical and optical properties of the PbI2-
like materials depend on the presence of defects or vacancies,
which are produced during the incorporation of foreign atoms or
impurities at the interstitial sites. To achieve optimum working
performance, thin lms of this type material should exhibit
minimal defects/impurities. In this study, these types of defects/
impurities were removed by performing several repetitions of the
zone rening technique to enhance the performance of PbI2-
based devices by increasing the purity of the material [19].
PbI2 has a layered structure with a hexagonal unit cell,
wherein each lead atom is sandwiched between two iodine
atoms. The stacking of these sandwiched sheets forms a three-
dimensional crystalline polytypic structure along the third direc-
tion, due to weak bonding between the layers [2]. Several studies
have been reported on the optical, electrical and structural
properties of PbI2 thin lms and demonstrated that variations in
these properties depend on the thin lm preparation technique
[13]. Prior to this contribution, we were also reported on a PbI2
thin lm prepared using the thermal evaporation technique [13].
In addition, the effect of thickness on various properties of PbI2
thin lms prepared using a material puried by the zone rening
technique has been given the least attention by investigators.
In this investigation, the initial material was puried by the
zone rening technique and was subsequently used for the
deposition of thin lms with different thicknesses on top of
ultrasonically cleaned glass substrates via vacuum evaporation.

0022-3697/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jpcs.2012.04.019
1310 M. Shkir et al. / Journal of Physics and Chemistry of Solids 73 (2012) 13091313
The deposited lms were characterized by different techniques,
and the analysis of their properties is discussed.
2. Experimental
Commercially available lead iodide (PbI2) of 99.98 % purity was
placed in a 2.5 cm  7.5 cm. quartz boat and was treated in a
double zone rening apparatus (designed and developed at the
authors laboratory), as shown in Fig. 1. The translation speed of
the boat was maintained at 5 mm/hour for 32 cycles to achieve
maximum material purity. The rened material was cooled
slowly to room temperature and was ground up to produce a
ne homogeneous powder measuring 100 mm. The obtained
powder was further annealed at 250 1C for 48 hours and was
again converted into a ne powder for the deposition of the lms.
The preparation of thin lms was performed in a vacuum coating
unit (Model No-EYU-3000, VEQCO) under a vacuum of 5  10-6
Fig. 1. Schematic of the zone-rening set-up featuring the following components:
1, 2 heating zones, 3, 4, 6 motors and trolley for the translation of the heaters,
5 concrete plate-form, 7 quartz chamber, 8 charged quartz boat and 9, 10 inlet and
outlet for inert gases.
Fig. 2. XRD patterns of puried PbI2 materials.
torr. The prepared material was placed in a tungsten boat,
evaporated using an electrical lament heater and was condensed
on an ultrasonically cleaned glass substrate at room temperature.
The thickness of the lm was controlled by the amount of
material used in the deposition and the deposition time. Utmost
care was taken to avoid overheating the material to prevent the
decomposition of PbI2 during the sublimation, as well as to
maintain the stoichiometry of the compound in the lm. The
thicknesses of deposited thin lms were measured using a quartz
crystal thickness monitor and determined to be 100, 200, and
300 nm.
The powder X-ray diffraction (PXRD) patterns were recorded
using a Panalytical powder X-ray diffractometer (PW-1830) with
CuKa (1.54056 A) radiation, a Ni lter in the angular range of
5-701 and a step size of 0.021 [20]. All parameters were kept the
same for all samples. Scanning electron microscopy was per-
formed on thin lms using a ZEISS EVO SEM (EVO50). The optical
absorption of thin lms was measured as a function of wave-
length in the range of 200900 nm using a Perkin Elmer lambda
35 UV-Vis. spectrophotometer. The uorescence of thin lms was
measured using a Perkin Elmer LS-55 uorescence spectrophot-
ometer. The dc conductivity was measured with a Kithely elec-
trometer (6517) at different temperatures.
3. Results and Discussion
The powder X-ray diffraction pattern of puried PbI2 is
provided in Fig. 2. The PXRD patterns of thin lms prepared from
the puried material are provided in Fig. 3. From the PXRD, it is
evident that all deposited thin lms exhibit a crystalline struc-
ture. The sharpness of the peaks in the PXRD patterns indicates
that the deposited thin lms exhibited good crystallinity. The
2theta values were used as input for the conrmation of the
crystal system, and the lattice parameter calculations were
performed using the Proszki software. A single peak conrmed
that the prepared PbI2 thin lms exhibited a hexagonal structure
that is predominantly oriented along the o001 4 direction. In
addition, the data also conrm the presence of a single phase. The
determined unit cell parameters were a b 4.532 A, c 6.942 A,
and the space group was P-3m1. The crystallographic data for the
 M. Shkir et al. / Journal of Physics and Chemistry of Solids 73 (2012) 13091313 1311

Fig. 3. XRD patterns of PbI2 thin lms with different thicknesses.

thin lms in this study are in good agreement with the previously
reported data [2]. The size of the crystallites in these thin lms
was calculated using the following relation [21]:
D 0:94 l=b Cos y
where D is the grain size, l is the wavelength of the scattered
radiation, y is the scattering angle and b is the full-width at half
maxima (FWHM) of the diffraction peak. The calculated sizes of
the crystallites were found to be  5, 7 and 10 nm for the 100, 200
and 300 nm thin lms, respectively [Table 1]. The intensity of the
XRD peaks was also found to increase with increasing lm
thickness. These ndings clearly demonstrate that the size of
the crystallites and the crystallinity of thin lms increase with
increasing thickness.
As shown in Fig. 7, SEM micrographs of PbI2 thin lms with
1
different thicknesses reveal that the surface of the lms is notably
smooth and free of voids. The grains in these lms are crystalline
and homogeneously distributed. The thin lm thickness is uni-
form throughout the lm for all specimens. The surface morphol-
ogy of the thin lms varies with lm thickness. Fig. 7(a) depicts
the morphology of a 100 nm sample, which features a well-
covered surface with mustard seed-like grains. For lms with
1312 M. Shkir et al. / Journal of Physics and Chemistry of Solids 73 (2012) 13091313

Table 1
Structural and optical parameters of PbI2 thin lms with different thickness.

Thickness(t) Peaks FWHM Crystallite Grain size from Energy

(nm) angle (b2y) size from SEM (nm) Band gap
(Deg.) XRD (nm) (eV)

100 12.59 0.028 5 8 2.99

200 12.83 0.020 7 12 2.95
300 12.76 0.014 10 17 2.75

Fig. 5. Band gap variations of PbI2 thin lms with different thicknesses.

Fig. 4. Optical absorbance spectra of PbI2 thin lms with different thicknesses.

thicknesses of 200 and 300 nm, a rough surface was observed, as

shown in Figs. 7(b) and 7(c). The grain size of these thin lms was
found to be in the range of 817 nm [Table 1], which is consistent
with the size of the crystallites. All samples are crystalline, and
their crystallinity was found to increase with increasing lm
thickness [22].
The optical absorbance spectra of the deposited PbI2 thin lms
are provided in Fig. 4. The semiconductor properties of thin lms
are conrmed by the presence of a sharp absorption edge. The
optical energy band gap can be calculated using this well-known
relationship:
m intensity of EF bands is higher than that of EB bands, which may
a AhnEg =h n
where A is the characteristic parameter (independent of photon
energy) for the transitions, h is Planks constant, n is the
frequency of the light, Eg is the band gap and m is the parameter
that characterizes the process transition involved. The value of m
can be either 2 or 1/2 for the direct and indirect allowed
transitions, respectively. We used the value of m 2 because
PbI2 is a direct band gap material. The plots (ahn)2 as a function of
hn for all PbI2 thin lms are provided in Fig. 5. The energy band
gap values of thin lms were obtained by extrapolating a straight
line to the hn axis. The optical energy band gaps of thin lms with
thicknesses of 100, 200 and 300 nm were found to be 2.99, 2.95
and 2.75 eV, respectively [Table 1]. These results demonstrate
that the band gap decreases with increasing lm thickness [2].
This result may be due to a change in the size of the crystallites/
grains. The band gaps of these thin lms are in good agreement
with the previously reported values [23].
The photoluminescence spectra of PbI2 thin lms (excited at
345 nm) are provided in Fig. 6. All of the lms exhibit two
emission peaks: one at  2.73 eV (EF) attributed to free excitons
Fig. 6. Photoluminescence spectra of PbI2 thin lms with different thicknesses.
and a second at 2.67 eV (EB) attributed to bound excitons. The
2
be due to the recombination of the free excitons with the band to
band transition. The intensity of these bands is directly related to
higher-order crystallinity, which is consistent with the XRD and
SEM results. J. F. Condeles et al. [16] also reported similar
observations for the PbI2 thin lms. Interestingly, as the lm
becomes thicker, the intensity of the near-band-edge emission
also increases. This result implies that the intensity of the near-
band-edge emission depends on the quality of the crystallinity of
the thin lm, wherein more crystalline thin lms produce
enhanced optical properties (Fig. 7).
The dc conductivity of PbI2 thin lms with different thick-
nesses is provided in Fig. 8. With increasing temperature
and thickness, the dc conductivity of thin lms was found to
increase. These results are consistent with the electronic proper-
ties of semiconductor materials. At low temperatures, most of the
free carriers in a semiconductor do not have sufcient energy to
jump from one level to another level. When the temperature
increases slowly, the carrier concentration increases in the
conduction band, resulting in an increase in the dc conductivity
with increasing temperature [24].
 M. Shkir et al. / Journal of Physics and Chemistry of Solids 73 (2012) 13091313 1313

100nm 35

30

25

dc ( m)-1x10-9
20

15

10

200nm 5

Temperature (C)

Fig. 8. dc Conductivity of PbI2 thin lm with different thicknesses.

Acknowledgments

The authors acknowledge the Director of NPL, Prof. M.A. Wahab,

Head, Dept. of Physics, JMI and Dr. G. Bhagavannarayana, scientist G
of NPL for their fruitful discussions. Author Dr. Mohd. Shkir/Shakir
300nm acknowledges the Director, Dean, MRCE and the principal and co-
coordinator, ARSD College, DU for their continuous encouragement.

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