Indian Journal of Pure & Applied Physics

Vol. 50, June 2012, pp. 380-386

Structural and optical properties of ZnS, PbS, Zn1−xPbxS, ZnxPb1−xS and

PbZnxS1−x thin films
Mahdi Hasan Suhail
Department of Physics, College Of Science, University of Baghdad, Iraq
E-mail: mhsuhail@yahoo.com
Received 9 May 2011; revised 6 February 2012; accepted 10 April 2012

The chemical spray pyrolysis technique (CSPT) to prepare ZnS, PbS, PbxZn1−xS, (x=0 to 1), PbZn1−xSx and PbxZn1−xS,
thin films with (x = 0.01, 0.02) at glass substrate, has been used. The result of X-ray diffraction obtained that the films are
polycrystalline and have cubic with hkl (111) and wurtize with hkl (100) phases for ZnS films, the phase for PbS films is
cubic with hkl (200) and the phases for PbxZn1−xS, Pb1−xZnxS and PbZnxS1−x are cubic with hkl (200). The lattice constants
(a) have been calculated as 5.939Å for PbS films, 3.36Å and 5.44Å for wurtize and cubic of ZnS films, respectively, 5.91 to
6.2Å as x varied from 0 to 1 for Zn1−xPbxS,5.92Å for ZnxPb1−xS films with x = 0.02, and 5.921Å for PbZnxS1−x films with x =
0.01. The absorption spectra used in the wavelength range 200-1100 nm to calculate the optical energy gap which is found
to decrease with increase in the film thickness for all the films prepared by this technique. The values of energy gap have
been determined and it was between (1.58-1.78 eV) for PbS films, (2.9-3.1eV) for ZnS films. The energy gap of ZnxPb1−xS
films in the range (2.4-2.9
eV and (2.38-2.75) eV and of PbZnxS1−x it was (1.57-1.8
eV and (1.4-1.6
eV for x = 0.02 and x
= 0.01, respectively as the thickness increases. The optical constants, such as refractive index (n) and extinction coefficient
(k) increase and decrease with increase in the film thickness, respectively for all the films except ZnS films which are having
inverse properties. The dielectric constants (r, i) have the same behaviour of refractive index (n) and extinction coefficient
(k), respectively.
Keywords: Optical properties, Structural properties, Energy gap, Semiconductor thin film, ZnS thin film, PbS thin films

1 Introduction There are many techniques that have been used to

Semiconductor materials are always the focus in
material science due to their outstanding electronic
and optical properties and extensively potential
application in various devices including light-emitting
diodes, single electron transistors and field-effect
thin-film transistors. In principle, the electronic and
optical properties of semiconductor materials are
tunable by varying their shapes and sizes so it is one
of the desired goals in material science to realize
precise control of the morphology of semiconductor
materials1.
ZnS an important semiconductor material with
large band gap (3.5 eV), high refractive index (2.35 at
632 nm) high effective dielectric constant (9 at 1
MHz). It’s optical properties make it useful as a filter,
reflector and planar wave guide2. A number of
techniques have been examined in the search for more
reliable and cheapest method of producing thin films.
Physical and chemical depositions are the most
common methods for transferring material atom by
atom from one or more sources to the growth surface
of a film being deposited onto a substrate. So we have
two general methods which are the physical and
chemical depositions3-5.
prepare thin films. Among the various thin film
deposition techniques, chemical spray pyrolysis
technique (CSPT) is one of the principle methods to
produce large area and uniform coating6,7 and deposit
a wide variety of materials in thin film form. The
prime requisite for obtaining good quality thin film is
the optimization of preparative conditions viz.
substrate temperature, spray rate, concentration of
solution etc.
The interest to non-vacuum methods for thin films
deposition has increased in the last decade. The
solution based process has several advantages:
simplicity of process, access to a wide range of metal
oxide stoichiometries, precise composition control
and applicability to substrate at any size.
Two of the most important optical properties are
the refractive index n and the extinction coefficient k,
which are, generally, called optical constants.
Using the fundamental relations of photon
transmittance T and absorbance A,
It = Io exp (−t) … (1)
 SUHAIL: STRUCTURAL AND OPTICAL PROPERTIES OF THIN FILMS 381

where It is the incident photon energy at thickness (t) r = n2 – k2 …. (12)

inside the material and Io is incident photon energy at
surface of material8. i = 2nk … (13)
and
2 Experimental Details
A=log Io/It … (2) Before starting the deposition, the solutions are
mixed according to the film components, (after found
we have
their weight by this equation (W=M×Mwt×V/1000,
= 2.303 A/t … (3) where M is the molarity, Mwt the molecular weight, V
is the volume), the solutions can be prepared by
The reflectance (R) has been found by using the solving the salts in the distilled water as follows:
relationship
Thiourea solution CS(NH2)2: This solution can be
R+T+A = 1 … (4) prepared with molarities (0.1 M), from solving
(0.761 g) of thiourea in (100 mL) of distilled water.
For normal reflectance, we have9,10 Lead acetate solution Pb(CH3COO)23H2O: This
solution can be prepared with molarities (0.1 M),
R= (n−1)2 / (n+1)2 … (5) from solving (2.78 g) of lead acetate in (100 mL) of
distilled water.
By using the above relation, the refractive index
ZnSO47H2O solution: This solution can be prepared
can be determined from the relation:
with molarities (0.1 M), from solving (2.87 g) of
ZnSO47H2O in (100 mL) of distilled water.
n = (1+(R)1/2)/(1−(R)1/2) …(6)
After getting the different amount of solutions
The extinction coefficient is related to the according to the ratio and volume requirement, we put
absorption coefficient k by the relation 11. it on the magnetic stirrer for about 15 min to be sure
solutions have been mixed properly. After cleaning
k =/4 … (7) the substrates, we place them on the electrical heater
surface and leave them for about 15 min so as their
where  is the incident photon wavelength. temperature reaches the electrical heater temperature.
The absorption of radiation that leads to electronic The solution must be put in solution container after
transitions between the valence and conduction bands that we can start the deposition process. The substrate
is split into direct and indirect transitions,these heater was an electrically controlled block furnace.
transitions are described by the equation12,13. After the spray process has been completed, we leave
the substrate on the surface of heater about 20 min in
α(hυ) = A* (hυ − Egop )r … (8) order to see that chemical interactions and the
crystallization process are complete.
where h is the incident photon energy, Egop: is optical The structural analysis of the film has been studied
energy gap, and r is constant which takes the values by using X-ray diffraction system (XRD-6000-
(1/2, 3/2, 2, 3) depending on the material and the type Shemadzu) operating with 0.15418 nm
of the optical transition whether it is direct or indirect. monochromatized Cu-K radiation at 40 kV and 30
The real and imaginary parts of dielectric constant mA with Ni filter. The UV/VIS/NIR spectroscopy
(r and i, respectively) can be calculated as follows12: type Shimadzu was used to measure the absorption of
prepared films from wavelength 200 nm up to 1100
N* = n−ik … (9)
nm and so that thickness of thin films,the energy gap
Complex dielectric constant and absorption coefficient can be calculated. The
extinction coefficient and the refractive index of
* = r – i i..… … (10) prepared thin films have been measured by using Eqs
(3 and 6), respectively. The real and imaginary parts
From the relation N*=*, therefore:
of the dielectric constant have been measured by
(n – ik) 2 = r−i εi … (11) using Eqs (12 and 13), respectively, under the
conditions of normal incidence, room temperature and
So that uncoated glass slide.
382 INDIAN J PURE & APPL PHYS, VOL 50, JUNE 2012

3 Results and Discussion the film thickness increases which are due to the
different effective thickness of the thin films16.
3.1 Structural and optical properties of ZnS films Table 1 presents the values of the real and
3.1.1 X-ray diffraction results imaginary parts of the dielectric constant at 600 nm
It is observed that for ZnS film of thickness (1300) wavelength and have the same behaviour of refractive
nm was found to exhibit diffraction peaks associated index and extinction coefficient.
with (100), (002) (101) and (103) reflections for the
hexagonal structure and (014) reflection for the cubic 3.2 Structural and optical properties of PbS films
structure of which the intensity of the (014) 3.2.1 X-ray diffraction results
orientation is predominant (Fig. 1 ). For PbS film of thickness (1038) nm, it was
The lattice constant (a) for ZnS thin films was observed from Fig. 2 that five diffraction peaks
(3.36Å) for wurtize hexagonal structure and (5.44Å) associated with (111), (200), (202), (311), and (222)
for cubic phase which are found to be in agreement also there are another two weak peaks associated with
with the result obtained by Ubale et al.9. for ZnS films (400) and (331) are shown. All the diffraction peaks
by chemical bath deposition using thiourea and zinc can be indexed to a face-centered-cubic rock-salt-
acetate as S−2 and Zn+2 source. structured PbS which coincide with the work of Ken-
Tye Yong et al. whose study is of PbS Nanowires17.
3.1.2 Optical characteristics
The different peaks for PbS film are indexed in
It is observed that the optical energy gap decreases
with increase of film thickness, as listed in Table 1. Table 1 — Values of refractive index (n), extinction coefficient
(k), real (r) and imaginary (i) dielectric constant for ZnS films
This may be due to the possibility of structural defects (at 650 nm wavelength)
in the films arisen during the time of their preparation,
which could give rise to the allowed states near the Thickness n K*10−4 r i Eg(ev)
conduction band in the band gap. In the case of much (nm)
thicker films, these allowed states could well merge 797 1.304 19 1.708 0.004 3.1
with the conduction band resulting in the reduction of 1036 1.282 12 1.640 0.003 3.0
the energy band gap14. This is similar to the results of 1306 1.274 09 1.620 0.002 2.9
many other researchers like Nadeem and Ahmed4 for Table 2 — Comparison of crystallographic data for PbS thin
ZnS thin films which were prepared by Resistive films with the JCPDS card 5-592 ( Ref.18)
Heating Technique. Standard data Observed (d) and (a) value for PbS film
The refractive index was determined from the d (Å) hkl d (Å) hkl a (Å)
reflectance data and listed in Table 2. The increase of 3.429 111 3.429 111 5.939
the film thickness causes an overall decrease in the 2.969 200 2.974 200 5.948
refractive index. The decrease is due to the overall 2.099 202 2.100 202 5.939
decrease in the reflectance with the increase of film 1.790 311 1.792 311 5.943
1.712 222 1.718 222
thickness. This behaviour is similar to the work of 1.483 400 1.486 400
Ubale et al.9 for ZnS thin films by thermal 1.361 331 1.362 331
evaporation technique. The variation of extinction
coefficient with the photon wavelength decreases as

Fig. 1 — X-ray diffraction pattern for ZnS thin film Fig. 2 — X-ray diffraction pattern for PbS thin film
 SUHAIL: STRUCTURAL AND OPTICAL PROPERTIES OF THIN FILMS 383

Table 2 as well as the corresponding values of the From Table 3, we can observe that the refractive
interplanar distance dhkl and compared with the index increases with increase of the thickness but not
standard values of ASTM data. systematically this is due to reflectance. The
The lattice constant (a) for PbS thin films was extinction coefficient decreases as the film thickness
5.939Å. This value is found to be in good agreement increases which is due to the different effective
with the standard value as shown in Table 2 which is thickness of the thin films, but not systematically as
5.94Å. No obvious characteristic diffraction peaks given in Table 3. This behaviour is similar to the work
from other impurities can be detected. The strong and of Debnath et al.20 thin films using Electron Beam
sharp diffraction peaks suggest that the as-obtained Evaporation Technique. The real and imaginary parts
products are well crystalline. of the dielectric constant for PbS thin films show in
Table 3 and have the same behaviour of refractive
3.2 1 Optical characteristics index and extinction coefficient.
It is observed from Table 3 that the optical energy
gap decreases with the increase of film thickness this 3.3 Structural and optical properties of Zn1−−xPbxS films
behavior is similar to result of Ubale et al.9 and 3.3 1 X-ray diffraction results
energy gap is found to be in the range 1.88-2.28 eV, X-ray diffraction pattern for Zn1−xPbxS film (x = 0
while the energy range found by the authors is in the to 1) was carried out with thickness 2000 nm and
range 1.58-1.78 eV. This difference refers to our shown in Fig. 3.
thicker films and different technique. The 100% intensity of peak (200) and lattice
constant of these peak are listed in Table 4. The value
Table 3 — Values of refractive index (n), extinction coefficient
(k), real (r) and imaginary (i) dielectric constant for PbS films of dhkl and lattice constant increase with increasing the
(at 650 nm wavelength) amount of zinc in the compound (Table 4).
Thickness n K*10-4 r i Eg (ev) 3.3.2 Optical characteristics
(nm) From Table 5, it can be observed that the refractive
550 1.424 44.78 2.028 0.0127 1.78 index and the extinction coefficient increase with
710 1.424 34.45 2.028 0.0098 1.68 increase in the thickness which is due to the different
880 1.484 35.20 2.203 0.0104 1.58
effective of the amount of lead in the films.
The variations of the real and imaginary parts of the
dielectric constant with the incident photon
wavelength show increase with increase in the amount
of the lead in the film. The absorption coefficient has
a high value at low-wavelengths (visible region) and
starts decreasing gradually towards the high
Table 4 — Crystallographic data for Zn1−xPbxS thin films

Standard data Observed (d) and (a) value for Zn1−xPbxS film
d (Å) hkl d (Å) Concentration (x) a (Å)
2.96 200 2.955 1 5.91
2.96 200 2.966 0.8 5.932
2. 96 200 2.972 0.6 5.944
2. 96 200 2.977 0.4 5.9543
2. 96 200 3.01 0.2 6.02
2. 96 200 3.012 0 6.20
Table 5 — Values of refractive index n, extinction coefficient k,
real r and imaginary i dielectric constant for Zn1−xPbxS films
with x=0.01 at 700 nm wavelength

Concentration (x) n K*10-4 r i Eg (ev)

0.2 1.32 62 2.1 0.046 3.0
0.4 1.38 92 2.3 0.042 2.84
0.6 1.45 126 2.7 0.035 2.68
Fig. 3 — X-ray diffraction pattern for Zn1−xPbxS thin film 0.8 1.48 162 3.1 0.025 2.40
384 INDIAN J PURE & APPL PHYS, VOL 50, JUNE 2012

wavelength of the ZnS thin films. But when you add film are indexed in Table 6 as well as the
the amount of lead to the film, according to the values corresponding values of the inter planar spacing
of x, we observed that we get shift in the edge d(hkl) and compared with the values of PbS film
absorption, where the value at x = 0 the edge at (111), (200), (202), with d value 3.418Å, 2.965Å and
wavelength 380 nm and pushed towards the 2.095Å, respectively and with obvious characteristic
wavelengths 600 nm when x = 0. 9, and this deviation diffraction peak from impurities from which can be
is causing the change in the energy gap. When we detected another unknown peak with its (2 = 33.278)
increase the amount of lead in the film we note that d value is 2.690Å which is due to the ratio of Zn. The
the energy gap decreases gradually to reach at x = 0. 9 lattice constant (a) for ZnxPb1−xS thin films is 5.92Å
to 2.43 eV. which is less than the lattice constant for PbS film due
This is attributed to the fact that the force bond of to existence of Zn. From Table 6, we can see that
S-Zn is found to be greater than the force bond of adding the Zn to the PbS leads to decrease the lattice
S-Pb. This result is because the zinc has constant.
electronegativity larger than for the lead. The
difference in electronegativity for bond S-Zn is 0.9 3.4.2 Optical characteristics
while the difference in electronegativity of the bond Decrease in extinction coefficient and imaginary
S-Pb is 0.3. Therefore, the energy required to break dielectric constant with increase the film thickness,
the bond S-Zn is higher than the energy need to break this is due to the effect of different thickness. It’s
the bond S-Pb, in addition to the lead has atomic energy gap decreases with increase in the film
number (82) which is greater than zinc (30), and the thickness and it is in the range 2.38-2.75 eV. At
large number of atomic electrons means that the link x = 0.02, there is the same behaviour of optical
be less to the nuclei which led to the transfer of an constants for ZnxPb1−xS with x = 0.01 9 (Table 7). It is
electron in an atom-level external lead easier than observed from Table 8 that the optical energy gap
electrons transfer to levels of an atom of zinc. decreases with the increase of film thickness. The
energy gap of ZnxPb1−xS films in the range 2.4-9 eV.
3.4 Structural and optical properties of ZnxPb1−xS films
3.4.1 X-ray diffraction results Table 6 — Comparison of crystallographic data for ZnxPb1−xS
thin films with PbS film
X-ray diffraction pattern for ZnxPb1−xS film (x =
0.02) was carried out with thickness1500 nm and Obser ved (d) and (a) value for Observed (d) and (a) value for
shown in Fig. 4. All the different peaks for ZnxPb1−xS PbS film ZnxPb1−xS film
d (Å) hkl a (Å) d (Å) hkl a (Å)
3.429 111 5.939 3.418 111 5.92
2.974 200 5.948 2.965 200 5.93
2.100 202 5.939 2.095
202
5.925
2.690 unknown
Table 7 — Values of refractive index n, extinction coefficient k,
real r and imaginary i dielectric constant for ZnxPb1−xS films
with x=0.01 (at 700 nm wavelength)

Thickness (nm) n K*10-4 r i Eg(eV)

790 1.411 37 1.992 0.0107 2.75

1030 1.417 29 2.009 0.0084 2.62
1300 1.421 24 2.078 0.0068 2.38
Table 8 — Values of refractive index n, extinction coefficient k,
real r and imaginary i dielectric constant for ZnxPb1−xS films
with x=0.02 (at 700 nm wavelength)

Thickness (nm) n K*10-4 r i Eg (eV)

790 1.31 23 1.72 0.0061 2.9
Fig. 4 — X-ray diffraction pattern for ZnxPb1−xS thin film 1030 1.40 28 1.96 0.0078 2.6
(x = 0.02) 1300 1.53 36 2.34 0.0112 2.4
 SUHAIL: STRUCTURAL AND OPTICAL PROPERTIES OF THIN FILMS 385

Table 9 — Comparison of crystallographic data for PbZnxS1−x

thin films with PbS film
Observed (d) and (a) for PbS Observed (d) and (a) for
films PbZnxS1−x films
d (A˚) hkl a (Å) d (Å) hkl a (Å)
3.429 111 5.939 3.419 111 5.921
2.974 200 5.948 2.965 200 5.930
2.100 202 5.939 2,094 220 5.922
Table 10 — Values of refractive index n, extinction coefficient k,
real r and imaginary i dielectric constant for PbZnxS1−x films
with x=0.01 (at 700 nm wavelength)

Thickness (nm) n K*10-4 r i Eg (eV)

Fig. 5 — X-ray diffraction pattern for PbZnxS1−x thin film 790 1.324 364 1.754 0.0096 1.4
(x = 0.01) 1030 1.451 341 2.105 0.0144 1.5
1300 1.465 360 2.148 0.0096 1.6
The optical behaviour of a material is, generally,
Table 11 — Values of refractive index (n), extinction coefficient
utilized to determine its optical constants [i.e.
(k), real (r) and imaginary (i) dielectric constant for PbZnxS1−x
refractive index (n), extinction coefficient (k), real films with x=0.02 (at 700 nm wavelength)
(r), and imaginary (i) dielectric constants]. From
Table 8, it can be observed that the refractive index Thickness (nm) n K*10-4 r i Eg (eV)
and the extinction coefficient increase with increase in 790 1.355 42 1.8369 0.0115 1.57
the thickness as listed in Table 8 which is due to the 1030 1.370 35 1.8777 0.0096 1.64
different effective thickness of the thin films. The 1300 1.467 42 2.1547 0.0125 1.80
variation of the real and imaginary parts of the
dielectric constant with the incident photon film. Also from Table 9, it could be seen due to
wavelength shows increase with increase in thickness. existence of Zn, lattice constant would decrease.
From Tables 4 and 6, we can see that due to
decrease in the ratio of Zn the optical constants 3.5 2 Optical constants of PbZnxS1−x thin films at (x= 0.01, 0.02)
increase. While the energy gap decreases with The optical constants for compound PbZnxS1−x for x
decrease in Zn ratio this behaviour is a good = 0.01, 0.02 are shown in Tables (10 and 11).The
agreement with the result of Al-Ajubory for refractive index increases with increase in film
ZnxPb1−xS films which were prepared by spray thickness while extinction coefficient decreases with
pyrolysis technique21. increase in film thickness and both real and imaginary
dielectric constants have the same behaviour of
3.5 Structural and optical properties of PbZnxS1−−x films refractive index and extinction coefficient,
respectively.The energy gap decreases with increase
3.5.1 X-ray diffraction results in film thickness.
X-ray diffraction pattern for PbZnxS1−x film (x = It can be seen that increasing Zn ratio leads to
0.01) was carried out with X-ray diffraction in the increase in the energy gap (Tables 10 and 11). The
range 2 between 20° to 50° as shown in Fig. 5. It is energy gaps for PbZnxS1−x with x = 0.01, 0.02 are
observed from Fig. 5 that for PbZnxS1−x film of closed to the energy gap of PbS films because the
thickness (1500) nm was found to exhibit three ratio of Zn is very small as compared to ratio of Pb
diffraction peaks associated with (111), (200), and and S.
(202), with d value 3.419, 2.965 and 2.094Å,
respectively. All the diffraction peaks can be indexed 4 Conclusions
to a face-centered-cubic rock. The different peaks for The following conclusions may be drawn from the
PbS film are indexed in Table 9 as well as the results obtained: XRD-studies showed that all films
corresponding values of the interplanar spacing d are polycrystalline with cubic phase except ZnS films
(hkl) and compared with the PbS film. have cubic and hexagonal phase. Optical studies
The lattice constant (a) for PbZnxS1−x film was reveal that these films have a direct band gap and it is
5.921Å which is close to the lattice constant of PbS observed that the bad gaps decrease with increase in
386 INDIAN J PURE & APPL PHYS, VOL 50, JUNE 2012
the film thickness. The transmittance is high in vis-
NIR regions and the high transmittance properties
make film a good material for thermal control
window coating for cold climates and anti-reflective
coating. The refractive index (n) increases with
increase in the film thickness, while the extinction
coefficient (k) decreases with increase in the thickness
for all the films except ZnS films which are inversely.
Spray pyrolysis method for production of the solid
films is a good method for preparation of thin films
suitable for scientific studies and for many
applications in technology and industry.
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