Optical Materials xxx (2013) xxxxxx

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Structural, optical and light scattering properties of post etched RF sputtered

ZnO:Al thin lms deposited at various substrate temperature
Venkateswarlu Bhavanasi a,c, Chandra Bhal Singh a,d,, Debjit Datta a,b, Vandana Singh a, Keshawa Shahi b,c,
Satyendra Kumar a,b
a

Samtel Centre for Display Technologies, IIT Kanpur, Kanpur 208 016,UP, India
Department of Physics, IIT Kanpur, Kanpur 208 016,UP, India
Material Science Programme, IIT Kanpur, Kanpur 208 016,UP, India
d
SSN Research Centre, SSN Nagar, Kalavakkam 603 110, TN, India
b
c

a r t i c l e

i n f o

Article history:
Received 21 May 2012
Received in revised form 14 January 2013
Accepted 30 January 2013
Available online xxxx
Keywords:
ZnO thin lms
Light scattering properties
Dislocation density
Urbach energy
RF magnetron sputtering
Wet chemical etching

a b s t r a c t
ZnO thin lms have become prominent material because of its application in solar cells as front contact.
The light scattering capacity of the front contact is important in achieving high efciency of the solar
cells. Here ZnO:Al lms deposited by reactive RF magnetron sputtering of the ZnO target doped with
2% Al2O3 by varying the substrate temperature is presented. Decrease in dislocation density with increasing substrate temperature indicates the improvement in crystalline nature of lms. Optical band gap,
Urbach energy and refractive index of lms are correlated with structural changes (grain size and strain)
in lms with increasing substrate temperature. The as deposited lms (at different substrate temperatures) are smooth giving rise to no scattering of light. After the lms were etched in 0.5% diluted HCl
for 15 s the light scattering capacity improved. The morphological studies of as-deposited and etched
lms show that substrate temperature has a strong effect on the developed surface morphology, and
hence on the light scattering properties. The lm haze, which is a measure of light scattering capability,
increased from 0.1 to 0.66 with increasing the substrate temperature from room temperature to 300 C.
The etched lm deposited at 5  104 mbar deposition pressure and 200 C temperature shows a maximum haze value of 0.8 at 400 nm. The increased light scattering ability of lms explained in terms of
Urbach energy which is a measure of structural disorder in lm surface.
2013 Elsevier B.V. All rights reserved.

1. Introduction
ZnO based transparent conducting oxides (TCOs) are vital for
the silicon based thin lm solar cells compared to other TCOs
(ITO, etc.) due to its high transparency and resistance to hydrogen
plasma [1]. The front contact TCO made by ITO or SnOx is reduced
into In or Sn in presence of hydrogen plasma. The oxygen released
in this process mixes with silane gas and leads to formation of
SiO2/a-Si:H mixture at the interface and thus deteriorate the structural, optical and transport properties of TCO [2,3]. Chantarat et al.
reported that Al doped ZnO lms conserve the structural and transport properties of TCO lms [4]. Another important parameter
essential in silicon based cells is the effective light trapping. This
can be achieved by using a textured ZnO (TCO) thin lm as front
contact. Various techniques are available for the deposition of
ZnO thin lms: Solgel [5,6], chemical vapor deposition [7], atomic
layer deposition [8], pulsed laser deposition [9], spray pyrolysis
Corresponding author at: SSN Research Centre, SSN Nagar, Kalavakkam 603
110, TN, India. Tel.: +91 8939402621; fax: +91 44 27469772.
E-mail address: cbs.sbc@gmail.com (C.B. Singh).

[10], molecular beam epitaxy [11], metal organic chemical vapor

deposition [12] and sputtering (DC, RF) [13,14] are commonly
used. It is reported that RF magnetron sputtering technique allows
depositing higher quality ZnO lms after controlling the deposition
parameters [15]. Silicon solar cells show lower conversion efciency as compared to crystalline silicon solar cells. It is reported
that the conversion efciency of silicon thin lm solar cells can
be increased by light absorption enhancement [16]. So, a light
management technique such a texturing of lm surface is suggested to increase the optical path inside solar cells. At textured
lm surface, the light propagation direction randomizes inside
the material due to total internal reection and results in longer
optical path [17]. Various techniques such as randomly, periodically textured surface and photonic crystal structures are used to
increase the optical path length and thus absorption in the absorber layer [18,19].
Zhu et al. [20] used two step etching using HF and HCl to study
the light scattering properties of ZnO:Al lms while Xen [21] used
HCl, oxalic acid and KOH mixture to etch pulsed dc magnetron
sputtered ZnO:Al lms. Kluth et al. [22] reported the different surface textures developed upon etching in weak hydrochloric acid.

0925-3467/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.optmat.2013.01.037

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They have correlated sputter parameters, lm morphology and

etching behavior of RF sputtered ZnO:Al and successfully applied
these lms in solar cells and observed high quantum efciencies
in the long wavelength range [22,23]. The surface features of lms
depend on the deposition conditions. Yoo et al. reported the effect
of substrate temperature and argon pressure on the structural,
electrical and optical properties of ZnO thin lms and post etching
behavior [24]. At low pressures (<2.7  103 mbar) and high-substrate temperatures (300 C), the surface morphology of the lms
exhibited a denser and compact lm structure with effective
light-trapping to apply for the fabrication of thin lm silicon solar
cells. Berginski et al. studied the effect of vacuum annealing and
different aluminum doping concentrations of target along with
substrate temperature on the properties of post textured ZnO thin
lms and hence on the cell efciencies [25]. Three essential parameters in sputtering that affect the lm properties are substrate temperature, working pressure and deposition rate [26]. Here the
effect of substrate temperature on post etching behavior of ZnO:Al
lms prepared by reactive magnetron sputtering has been examined. Simultaneously the effect of substrate temperature on structural optical and light scattering properties of ZnO:Al thin lms
before and after etching has been studied. The objective of this
work is to prepare high transmittance ZnO:Al lms with well light
scattering properties.

2. Experimental detail
ZnO:Al thin lms have been deposited on glass by RF magnetron sputtering using ZnO target doped with 2% Al2O3. ZnO:Al target is commercial target purchased from Kurt J. Lesker. Prior to
the deposition, the substrates were ultrasonically cleaned using
de-ionized water, chromic acid, DI water, acetone, Tri-chloro ethylene, acetone, ethyl alcohol respectively and kept for 20 min in
hot oven at 150 C. For the cleaning of silicon substrates, in addition to the above procedure, silicon substrates immersed in buffer
solution of 5% hydrouoric acid and 95% methyl alcohol for
removing the native oxide. Argon and oxygen were used as sputtering and reactive gases. All depositions were carried out at
15 sccm of Argon (Ar) and 5 sccm of oxygen (O2) gas ow rate.
The applied RF power was 100 W. The base pressure was
8  106 mbar and deposition pressure was 8  103 mbar. The
distance between target and substrate was maintained 6 cm.
The substrate temperature was varied from room temperature
(RT) to 300 C. All the depositions were carried out for 90 min.
Wet chemical etching has been used to make the surfaces of
the lms textured to increase the light scattering properties.
The deposited ZnO:Al lms were etched in 0.5% HCl in DI water
for 15 s to improve the light scattering capability of the lms.
The thickness of the lms was measured by prolometer. The
crystallographic analysis of ZnO:Al thin lms has been done by
an X-ray diffractometer (Thermo Electron Model ARL XTRA) with
a copper source of wavelength (Cu Ka 1.541841 ), with a scan
speed of 3 per min, between 20 and 80 with a step size of
0.05. The XRD patterns are measured in grazing incidence mode
with 1 incident angle. With 1 incident angle we did not observe
the substrate contribution in all our lms. The XRD patterns are
analyzed for the orientation and the grain size of the deposited
lms. The surface morphology of the deposited and etched lms
is also studied by Secondary Electron Microscopy (SEM). To measure the light scattering property, optical properties (total and
diffused transmittance) of the lms were characterized by spectrophotometer (PerkinElmerUV/VIS Lambda 750) along with
integrating sphere (60 mm Labsphere). The ratio of diffuse to total
transmittance is known as haze, which is a measure of the light
scattering properties of the lms. The resistivity of The ZnO thin

lms are measured using the four probe method. The sheet resistance is rst calculated from the four probe method, and then by
multiplying it with thickness gives the resistivity value. In this
method the sheet resistance values are calculated using the following formula RS = 4.53 (V/I), where I is current owing through
the outer probes and V the voltage drop measure across the two
inner probes.
3. Results and discussions
ZnO:Al thin lms deposited using ZnO target doped with 2%
Al2O3. O2 gas was introduced along with argon during deposition,
and is found that the deposited lms are highly transparent
(around 85% on glass). No peel off is observed in these lms. We
examined the position of the substrates on the substrate holder
for achieving singly crystalline ZnO:Al lms. Wet chemical etching
of the deposited lms were done to achieve the textured surface
and so to improve the light scattering properties.
3.1. Positional dependence
While depositing ZnO thin lms with sputtering, the properties
of deposited ZnO thin lms strongly depend on the position of the
substrate relative to target. During sputtering, the ionic bombardment happens only at some area called the target erosion area (or
race track). Under the target erosion area, substrates are affected
by bombardment of energetic particles (ions, electrons, photons,
atoms), metastable as well as neutral particles having different rang
of energy [2729]. These energetic particles, ions, atoms collide with
surface of lms during sputtering and cause the structural, optical
and electrical properties of the lms [30,31]. Fig. 1 shows the different positions of the substrates. Glass substrates were placed under
and outside the erosion area of the target. The substrate temperature
was xed at 200 C during the deposition of lms. Table 1 shows the
deposition rate under and outside the erosion area. It is observed
that the deposition rate under the erosion area is higher than that
of the outside erosion area because the probability of the ejection
of the sputtered atoms in vertically down ward direction is larger
compared to that in all other possible directions [32].
3.1.1. Structural properties
The XRD pattern of the ZnO:Al lms deposited under and outside the erosion area is shown in Fig. 2a. While ZnO:Al lms deposited under the erosion area have multiple orientations such as
(1 0 0), (1 0 1), (1 1 0) and (1 1 2) with (1 0 0) as predominant one,
lms deposited outside the erosion area show a (0 0 2) preferred
orientation along with a weak (1 0 3) orientation. Based on XRD results, it can be ascertain that energetic particles (O, O2, Zn, and
+
ZnO), ions (O, O
2 , Ar ), photons and electrons during sputtering
process inuence the lms growth process and thus crystallographic orientation [29,32]. Fluxes of high energy oxygen atoms
and ions deteriorate the lm microstructure by creating adatom
absorption sites and trap in lms [32]. These energetic oxygen ions
(O-, O
2 ) usually generate under erosion area of target. These oxygen species cause irregular morphology in lms and reduce the
crystallinity and conductivity of lms. A similar phenomenon of
deterioration in ZnO lms under erosion area was also reported
by Lee et al. [29].
The crystallite size of the ZnO:Al thin lms is calculated from
the X-ray diffraction pattern using DebyeScherrer formula [34]

D 0:9k=b cos h;

where D is crystallite size, b is the corrected Full Width at Half Maximum (FWHM), h is the angle of diffraction and k is wavelength of
X-rays. The crystallite size calculated for the preferred orientation

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Fig. 1. Diffrent positions of the substrate: (1) inside the erosion area (inside the race track) (2) under the erosion area (under the race track), and (3) outside the erosion area
(outside race track) of the target.

(b) 100

Intensity (a.u.)

Under the erosion area

out side the erosion area
(002)
(103)
(100)

20

(c)

30

(101)

40

(110)

50

(112)

60

70

Transmittance & Reflectance (%)

(a)

80

2 (deg.)

(d)

Transmittance
80
Outside the erosian area
Under the erosian area

60

40

Reflectance
20

400

800

1200

1600

2000

Wavelength (nm)

Fig. 2. (a) XRD pattern of ZnO thin lms deposited under and outside the erosion area, (b) the transmittance and reectance of the lms deposited under and outside the
erosion area, (c) scanning electron micrographs of lms deposited under the erosion area and (d) deposited outside the erosion area.

is given in Table 1. It is observed that the crystallite size of the lms

deposited outside the erosion area is 20 nm which is greater than
the crystallite size, 12 nm, of the lms deposited under the erosion area. This may be due to the bombardment of energetic oxygen
with the top surface of substrates which may have resulted in re
sputtering of the deposited lm.
Fig. 2c and d shows the SEM images of the lms deposited under and outside the erosion area. From the images it is observed

that the lms deposited outside the erosion area is smooth compared to the lms deposited under the erosion area. It is also noticed that lms deposited under the erosion area contains grains
of different shape such as round, triangular, and elongated where
as the lms deposited outside the erosion area contains almost
spherical grains. This may be the abnormal growth of the lms
due to bombardment of the energetic species with top surface during deposition.

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3.1.2. Electrical resistivity

The resistivity of the ZnO thin lms were measured by four
probe method and are shown in Table 1. The resistivity of the lms
deposited under the erosion area is 515.2 X cm which is higher
than the lms deposited outside the erosion area (10 X cm). The
higher resistivity values of the lms deposited under the erosion
area compared to the lms deposited outside the erosion area is
due the traps in lm surface formed by high energy species and reduced poor crystallinity of the lms under the erosion area. During
sputtering process, high energy oxygen particles sitting at the grain
boundary surface act as barriers for charge transport. Our results
are consistent with results of Minami et al. [33]. Trapping of high
energy neutral and inert gas species make lms porous and also
reason for increased resistivity [32].
3.1.3. Optical properties
Fig. 2b shows the transmittance and reectance of the ZnO lms
deposited under and outside the erosion area. The transmittance
and reectance of the lms deposited under and outside the erosion area is approximately equal and the transmittance of the lms
is 85%. There is no effect as such of positional dependence on the
transmittance and reectance values. The optical band gap of the
lms were calculated from the well known absorption expression
[35]

ahm Ahm  Eg 1=2 ;

where hm is the incident photon energy and A is the constant. The

intersection of the tangent of the linear portion of the absorption
curve on X-axis is taken as the band gap. The calculated optical band
gap values are given in Table 1. It is observed that the band gap of
the lms deposited under the erosion is 3.32 eV which is greater
than the band gap of the lms, 3.27 eV, deposited outside the plasma. Higher the band gap of the lms under the erosion area is may
be due to lesser grain size of the lms compared to the lms deposited outside the erosion area. So we found that the lms deposited
outside the erosion area have better crystallinity and lower resistivity compared to the lms deposited under the erosion area.
3.2. Substrate temperature variation
ZnO thin lms were deposited at RT, 200 C and 300 C substrate temperatures by keeping all other parameters constant. All
lms were deposited outside the erosion area to get better crystallinity and lower resistivity. The lms were then etched for 15 s in
0.5% HCl in DI water solution.
3.2.1. Structural studies
Fig. 3 shows the XRD patterns of the lms deposited at room temperature, 200 C and 300 C substrate temperatures. It is observed
that the lms deposited at room temperature (heating is only due
to plasma, 60 C) are strongly c-axis (0 0 2) oriented along with a
weak (1 0 3) peak. With increasing the substrate temperature the
intensity of (0 0 2) peak decreased while that of (1 0 3) peak increased. For the lms deposited at 300 the preferred orientation
changes from (0 0 2) to (1 0 3). The changes in the crystallographic

Table 1
Crystallite size, resistivity, band gap and deposition rate of the lms deposited under
and outside the erosion area (substrate temperature 200 C).
Characteristics

Under the erosion area

Outside the erosion area

Crystallite size
Resistivity
Band gap
Deposition rate

12 nm for (1 0 0)
515.2 X cm
3.32 eV
220 /min

20 nm for (0 0 2)
10.0 X cm
3.27 eV
140 /min

Fig. 3. XRD patterns of ZnO thin lms deposited at different substrate

temperatures.

structure with substrate temperature are also reported by OndoNdong et al. [36].
The lms deposited without intentional heating are strongly caxis oriented which indicates that the sputtered atoms have proper
kinetic energy and mobility to develop c-axis orientation and is
achieved by the bombardment of top surface of the lm with
highly energetic species [29]. Increasing the substrate temperature
causes an increase in mobility of the sputtered atoms, which aligns
in different directions by overcoming the self-shadowing effect
leading to decrease of c-axis orientation. This might be the reason
for change in crystalline structure with increasing the substrate
temperature. The crystallite size of lms is calculated from XRD
patterns using DebyeScherrer formula as described in Section 3.1.1. Without any additional substrate heating, the ZnO:Al
lms have crystallite size 21 nm which increased to 28.55 nm at
200 C substrate temperature. Crystallite size is increased to
around 36 nm at 300 C substrate temperature. Increase in crystallite size is due to increase in the mobility of the atoms at high temperature. Increase in crystallite size results in lower quantity of
crystallite or grains and shift in peak position. Decrease in intensity, dislocation density, micro-strain and FWHM of (0 0 2) peak
of ZnO:Al lms with increasing substrate temperature is observed
as given in Table 2. These observed changes in structural parameters may be due to changes in grain structure of lms with increasing substrate temperature. Our results are comparable with the
results obtained by Kim et al. [37]. The dislocation density of
ZnO:Al lms is calculated using the equation e = 1/D2, where D is
the crystallite size. Decrease in dislocation density with increasing
substrate temperature indicates the improvement in crystalline
nature of lm.
It is observed from XRD patterns that (0 0 2) peak position shift
towards higher angle with increasing substrate temperature. At
room temperature, the (0 0 2) peak is at 2h = 34.205 which is lower
than the standard value of bulk ZnO (34.42). The peak position of
(0 0 2) orientation at lower angle indicates the residual strain in
ZnO:Al lm. For lms deposited at 200 C substrate temperature,
(0 0 2) peak have attained the standard position at 34.42 while
for 300 C peak position is shifted to little higher value (34.46).
Change in the position of peak indicates the lattice stress in the
lm. As the substrate temperature is increased, the strain in the
lm is relieved. Similar behavior of stress in ZnO lms is reported
in another study by Menon et al. [38]. The variation in stress in ZnO
lms with increasing temperature may be due to increase in grain
size and lattice expansion as mentioned in literature [39,40]. Electrical resistivity of the lms is sharply decreased from 1370 X cm
to 6.6 X cm with temperature increased from room to 200 C. Further increase in temperature from 200 C to 300 C caused decrease

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Table 2
Various crystallographic parameters calculated from XRD results of ZnO:Al lms grown at different substrate temperatures (0 0 2 peak).
Substrate temperature

FWHM ()

Peak position (2h)

Intensity (Arb.)

Grain size (nm)

Dislocation density (1014)

Micro-strain e = b cot h/4

RT
200
300

0.39464
0.2916
0.2315

34.205
34.42
34.46

1100.5
257.6
78.4

21.09
28.55
35.98

22.48
12.26
7.73

5.59  103
4.11  103
3.26  103

in resistivity from 6.6 X cm to 1.4 X cm. Decrease in electrical

resistivity with increasing substrate temperature is correlated with
crystalline nature of ZnO:Al lms [36]. Decrease in FWHM with
substrate temperature is resulted in larger grain size. Larger grains
in lms result in decrease grain boundary scattering and thus decrease in the electrical resistivity is observed at higher temperature
[41].
The measured thickness of the lms deposited at room temperature (RT), 200 C and 300 C are 900 nm, 990 nm and 1000 nm
respectively. The thickness of etched lms deposited at room temperature (RT), 200 C and 300 C are 500 nm, 620 nm and 740 nm

respectively. Fig. 4 shows the SEM images of as-deposited and

etched ZnO:Al thin lms deposited outside the erosion area at
RT, 200 C and 300 C. The images a, c and e show the surface morphologies of as deposited ZnO lms, and the images b, d and f show
that of etched ZnO lms. From the morphology of as deposited
lms, it is observed that the lms are smooth.
After etching of these lms in 0.5% HCl for 15 s, it is observed
that the lm deposited at room temperature do not show any
changes in surface morphology (showing clear grain pattern) and
the effect of etching is only to reduce the lm thickness. But the
lms deposited at high temperatures show rough morphology

Fig. 4. SEM micrographs of ZnO:Al lms deposited outside the erosion area at different substrate temperatures (RT, 200 C, 300 C): (a, c and e) before etching and (b, d and f)
after etching.

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temperature can be related to increased lattice stress in lms. Variation in stress is due to deviation of preferred (0 0 2) peak position
from its standard position [47].
Urbach energy is the width of exponential absorption edge and
quanties the structural disorders in lms. The absorption coefcient near band edge obeys the Urbach rule

along with etch pits. Roughness of the etched surface increases

with increasing substrate temperature.
3.2.2. Optical studies
The specular component of transmittance and reectance of asdeposited lms at different substrate temperatures are shown in
Fig. 5. From the gure it is clear that all the lms (deposited at different substrate temperatures) are highly transparent (85%) and
have approximately equal values of transmittance and reectance.
Absorption coefcient optical band gap, Urbach energy, refractive
index and lm density of ZnO:Al lms (before and after etching)
are calculated from optical transmittance data and presented in Table 3. In transmittance data of all lms, a sharp absorption edge is
observed at 370 nm. As substrate temperature is increased to
300 C, the absorption edge shifts to lower wavelength. The
absorption coefcient of ZnO:Al lms is calculated from transmittance data using relation

aE 1=t lnT normalized E;

ahm a0 exphm=EU ;

where a0 is a constant and EU is the Urbach energy which interpreted as width of band tails [48,49]. Urbach energy EU is deduced
from reciprocal gradient of the linear region of the plotting ln a versus hm. Urbach energy of ZnO:Al lms is decreased from 132 meV to
114.6 meV as substrate temperature is increased to 300 C. Decrease in Urbach energy with increasing substrate temperature is
attributed to improvement in lm quality. After etching, ZnO:Al
lms have showed higher Urbach energy (147.43 meV). Higher value of Urbach energy of etched lms is due to origin of structural
disorders and defects in lms during chemical etching. Films deposited at higher substrate temperature have showed higher Urbach
energy after etching. Increase in Urbach energy from 147.43 meV
to 169.49 meV is observed for etched lms deposited at 300 C.
From these results, it can be concluded that lms containing larger
grain size are prone to have more structural disorders after etching.
Refractive index of the lms is estimated from transmittance
data using Swanepoels envelop method [50]. The real part of
refractive index n is estimated using relation

where t is the lm thickness and T is the transmittance of thin lm.

Here Fresnel reections and scattering losses are neglected. The
optical band gap is estimated from slope of linear region to the
(hm) axis in plotting (ahm)2 versus (hm). At room temperature, the
optical band gap of ZnO:Al lm is estimated around 3.28 eV. Optical
band gap is increased from 3.28 eV to 3.33 eV at 200 C substrate
temperature. Blue shift in optical band gap of ZnO:Al with increasing substrate temperature may be due to increase in carrier concentration as reported by Burstein [38,41,42] and later also reported by
Uthana et al. and Caparatelli [43,44]. Further increase in substrate
temperature from 200 C to 300 C is resulted in decrease in the
optical band gap (3.30 eV). The narrowing or redshift in band gap
of ZnO:Al lms at 300 C may be due to hybridization between
the orbital of the Al dopant and of the ZnO matrix [45]. He et al. related the widening and narrowing of band gap with strain in the
lm [39]. Strain in lms also depend on grain size, so grain size also
affect the band gap of lm [46]. The lower value of band gap of
ZnO:Al lms deposited at room temperature and 300 C substrate

n N N2  s2 1=2 1=2 ;

N 2s  T M  T m =T M  T m s2 1=2;
where s is the substrate refractive index, TM is the maximum transmittance and Tm is the minimum transmittance at certain wavelength. The refractive index of glass substrate is 1.52. Density of
the lms is calculated using expression

q kn2  1=n2 2;
where q is density of lm and k is the dielectric constant of lm.
Refractive index of as deposited ZnO:Al lms at room temperature
is estimated around 1.837 and lm density 3.865 at xed wavelength 625 nm. It is found that refractive index decreased to 1.788
with increasing substrate temperature to 200 C but further increased to 1.834 for lms deposited at substrate temperature
300 C. Lowering of lm density at 200 C can be related to increase
in band gap according to Mosss rule and correlation Eg  na = constant [51]. But this correlation between refractive index and band
gap did not satisfy for etched ZnO:Al lms as both optical band
gap and lm density decreased. It may be possible that for etched
lms, structural disorders and defects dominate over lm density.
After etching of ZnO:Al lms, it is observed from calculated optical
parameters that band gap, refractive index, lm density are decreased for lms deposited with increasing substrate temperature
while Urbach energy is increased. This indicates the increase in
structural disorder and roughness in lms after chemical etching.
The etched ZnO lms show a decrease in specular transmittance
and reectance as observed in Fig. 6. It is also noticed that the specular transmittance of etched lms decreases with increasing the

Fig. 5. Specular transmittance and reectance of ZnO:Al lms deposited at RT, 200,
300 C (Before etching).

Table 3
Experimental resistivity, optical band gap energy (Eg), Urbach energy (EU), refractive index (n) and lm density (q) of ZnO:Al lms before and after lm etching.
Before etching of ZnO:Al lm

After etching of ZnO:Al lm

TSubstarte

Resistivity (X cm)

Eg (eV)

EU (meV)

Eg (eV)

EU (meV)

RT (50 C)
200 C
300 C

1370
6.6
1.4

3.28
3.33
3.30

132.0
117.3
114.6

1.837
1.788
1.834

3.865
3.698
3.856

3.356
3.33
3.31

147.43
151.50
169.49

1.69
1.60
1.57

3.33
2.99
2.87

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Fig. 8. Haze of the etched lms deposited at RT, 200 and 300 C.
Fig. 6. Specular transmittance and reectance of ZnO:Al lms deposited at RT, 200,
300 C (after etching).

substrate temperature. This is due to the increase in surface roughness of etched lms, as observed from the SEM images. Rough surfaces increase the scatter loss and thus reduce the transmittance of
the lm.
Distance (TMTm) between maxima and minima at certain
wavelength in transmission curve is directly related to its refractive index as given in Eq. (5). When substrate temperature is increased to 200 C, Distance between maxima and minima
(TMTm) decreased from 0.89 to 0.746 and consequently density
also decreased from 3.87 to 3.7 while thickness increased from
900 nm to 990 nm. Further increases in substrate temperature
(300 C) increase the thickness of lms to 1000 nm and Distance
between maxima and minima (TMTm) also increased to 0.884
and density is increased to 3.86. So, term (TMTm) can be used to
understand the changes in density of lms in function of substrate
temperature.
The scattering ability of the lms is measured by measuring the
haze, which is calculated as ratio of diffuse transmittance to the total transmittance. As-deposited lms shows no diffuse transmittance (indicating no light scattering); whereas the etched lms
show diffuse transmittance. Fig. 7 shows the total and diffuse
transmittance of the etched lms. The total transmittance of the
etched lms deposited at RT and 200 C is slightly higher (87%)
than that of as deposited state, where as the total transmittance
of the etched lm deposited at 300 C is slightly lower (83%). This
may be due to the higher thickness of the etched lm deposited at
300 C compared to the etched lms deposited at RT and 200 C.
Diffuse transmittance of the etched lms increases with the

substrate temperature as shown in Fig. 7. The etched lm deposited at 300 C shows a maximum of 41% diffuse transmittance.
Accordingly, the haze values of the etched lms increased with
increasing deposition temperature as observed from Fig. 8. The increased diffuse transmittance and hence increased in haze is due to
the rough surface morphology developed by means of etching.
From Fig. 8, it is clear that increase in the substrate temperature
leads to increase in the light scattering ability of the lms and a
haze value 0.66 (at 400 nm) is achieved for the lm deposited
at 300 C.
4. Conclusions
This study investigated the changes of structural, optical and
electrical properties of ZnO:Al lms under and outside the erosion
area of target as well as different substrate temperature. Changes
in morphology and crystalline phase explained in terms of bombardment of high energetic species on lm surface and related to
subsequent changes in optical band gap and electrical resistivity.
The crystallization of ZnO:Al thin lms deposited by RF magnetron
sputtering technique highly depended on the substrate temperature in presence of oxygen reactive gas. Optical band gap, Urbach
energy, refractive index and density of lms are correlated with
structural changes (grain size, strain) in lms with increasing substrate temperature. All the deposited lms were relatively smooth
giving no scattering of light which show 85% transmittance.
Rough surface with etch pits and regular rough morphology (lunar
landscape-like) textures were developed by wet chemical etching
in 0.5% diluted HCl solution. The surface roughness and haze (from
0.1 to 0.66) of etched lms increased with increasing substrate
temperature. The lm deposited at 5  104 mbar and 200 C
showed a regular rough morphology (lunar landscape-like) with
a haze value of 0.8 at 400 nm. Films deposited at higher substrate
temperature show increased haze value which is related to increased grain size. The increased light scattering ability of lms explained in terms of Urbach energy which is a measure of structural
disorder in lm surface. This new study can be useful to improve
the solar cell efciency as well as in cost reduction.
Acknowledgments
The authors thank Samtel Center for Display Technology, Materials Science Programme and Department of Physics, IIT Kanpur,
India for providing various facilities.
References

Fig. 7. Total and diffuse transmittance of etched ZnO:Al lms deposited at RT, 200,
300 C.

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