Journal of Alloys and Compounds 768 (2018) 978e990

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Determination of valence and conduction band offsets in

Zn0.98Fe0.02O/ZnO hetero-junction thin films grown in oxygen
environment by pulsed laser deposition technique: A study of efficient
UV photodetectors
Karmvir Singh a, Neelam Berwal a, Ishpal Rawal b, Sajjan Dahiya c, Rajesh Punia c, *,
Rakesh Dhar a
a
Department of Physics, Guru Jambheshwar University of Science and Technology, Hisar, India
b
Department of Physics, Kirori Mal College, University of Delhi, Delhi, India
c
Department of Physics, Maharshi Dayanand University, Rohtak, India

a r t i c l e i n f o a b s t r a c t

Article history: Here we present ZnO based thin films deposited in oxygen environment by pulsed laser deposition
Received 2 April 2018 technique for UV photodetection applications. The valence and conduction band alignments are the key
Received in revised form parameter required in understanding the type of charge carrier participating in conduction process. The
24 July 2018
valence and conduction band offset measurements have been carried out using the X-ray photoelectron
Accepted 26 July 2018
Available online 29 July 2018
spectroscopy (XPS) on the pristine ZnO, Fe (2 wt%) -doped ZnO (Zn0.98Fe0.02O) and the hetero-junction of
Zn0.98Fe0.02O with ZnO (Zn0.98Fe0.02O/ZnO). XPS studies revealed that the valence band is upward shifted
with 0.37 eV, whereas, there is a downward shifting of
0.393 eV in the conduction band. Structural
Keywords:
Pulsed laser deposition
analysis of the deposited films has been done using X-ray diffraction studies, which revealed the poly-
Zn0.98Fe0.02O/ZnO hetero-junction crystalline nature of all the films having wurtzite crystal phase. AFM studies suggest that the size of the
UV photodetector grains decreases with Fe-doping in ZnO network due to different ionic radii of Zn and Fe. UVeVis studies
suggest the decrease in optical band gap with Fe-doping and hetero-junction formation. The optical band
gap energy has also been obtained from the fitting of experimental data of absorption spectra with Mott
-Davis's model and Hydrogenic excitonic model. Both the models are well corroborated with each other.
The photoconduction behavior of the deposited films has been analyzed under UV light. The pristine ZnO
film has a photoresponse of about 25% which is found to increase in Zn0.98Fe0.02O (~36%) film. The
responsivity values are found to be 1.56, 2.17 and 1.86 mA/W for the pristine ZnO, Zn0.98Fe0.02O and
Zn0.98Fe0.02O/ZnO thin films, respectively.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction
In last two decades, a colossal deal of interest has been attracted
by the ultraviolet photodetectors in both the research and develop-
ment activities for the realization of their applicability in space to-
space communication, missile plumes detection, environmental
monitoring, flame sensors and many more optoelectronic devices
[1e10]. Silicon is one of the most widely used and reliable semi-
conductor materials for the photodetectors because of its suitable
* Corresponding author.
E-mail addresses: rajeshpoonia13@gmail.com, rajeshpunia.phys@mdurohtak.ac.
in (R. Punia).
optical band gap, high speed detection, low density surface states and
matured manufacturing technology. But these devices have a limi-
tation of low optical bandgap (~1.1 eV) for UV photodetectors, leading
to the use of costly high pass optical filters to block low energy visible
and infrared photons [11e14]. Malik and Wade [12] used an Ag-SiO2-
Si capacitor structure for solar blind UV photodetectors, where
different thicknesses of silver based band pass filter are used to
optimize the spectral response in a UV wavelength region of
20 nme320 nm. Whereas, Mu et al. [13] designed and fabricate a
metal-dielectric (Al/Al2O3 and Ag/SiO2) ultraviolet band-pass filters
with high transmissivity for UV photodetector applications. This re-
sults in a significant reduction in the efficiency of silicon based UV
photodetectors [11e14]. On the other hand, wide bandgap

https://doi.org/10.1016/j.jallcom.2018.07.303
0925-8388/© 2018 Elsevier B.V. All rights reserved.
 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990
semiconductor materials, particularly metal oxides are emerged as
the potential candidates for UV photodetectors because of their
intrinsic visible blindness, strong chemical bonding and relatively
larger penetration depth for UV light [1,15e19]. For example, Zhang
et al. [15] observed a fast UV photoresponse with response and re-
covery times of 0.82 and 0.64 ms, respectively, under an illumination
intensity of 2.5 mW/cm2 for low temperature annealed ZnO thin film
prepared by radio frequency magnetron sputtering technique,
whereas, Young and Liu [16] studied UV photodetection ability of Mg-
doped ZnO nanorods under UV light of 365 nm and observed a
response time of 30.9s and recovery time of 39.7s. They are observed
a detectivity value of ~1.49  108 cmHz1/2W
1 for the Mg-doped ZnO
nanorods at an applied biased voltage of 1 V. In recent years, metal
oxides have also caught special attention because of their hetero-
structural forms used for different applications [20e30]. Rana et al.
[24] studied the multilayered heterostructural forms of MgZnO and
ZnO (MgZnO/ZnO) with different Mg concentrations (2, 4, 6, and 8 at
%) for UV photodetection and observed a highest responsivity of
~0.16 A/W for 2 at% doping under UV light of wavelength 365 nm at
an illumination intensity of 3.2 mW/cm2, whereas, Patel and Kim [28]
are used NiO/ZnO heterojunction for UV photodetection studies and
observed an ultrafast photoresponse time of ~19 ms. Apart from the
oxide/oxide heterostructural analysis for UV photosensors, organic/
metal oxide heterostructural forms are also used by some researchers
[29]. Chan et al. [29] are used the polyaniline/MgZnO bilayer for solar
blind deep UV photodetectors. It is well known that the recombina-
tion of photo-generated charge carriers in photodetectors can be
reduced by applying some external deriving force. But in case of
heterostructure, an internal built-in potential is developed at the
heterojunction, which plays a key role to induce an internal driving
force which helps to discard the recombination of photo-generated
electron
hole pairs at the film surface [20e24]. A thin hetero-layer
of thickness 5e10 nm is generally used to rectify the problem asso-
ciated with surface recombination in metal oxide and low penetra-
tion depth of UV light. However, for heterostructure based
optoelectronic devices, understanding of type of charge carriers
(electrons and holes) and their contribution in electronic properties
is very critical [24,25]. The electronic properties of a hetero-structure
are strongly dependent on the kind of conduction and valence band
alignment at the interface. The mismatching of the electronic struc-
tures of both the layers at the interface leads to change in potential
barrier height arises from valence or conduction band offsets (CBOs)
and hence responsible for the change in electrical properties of the
hetero-structured metal oxide films [25e27]. Thus, the understand-
ing of conduction and valence band offsets at the hetero-junction is
very crucial for such optoelectronic hetero-devices.
Out of the well studied metal oxide hetero-structure devices for
different applications including UV photodetection, ZnO stands out
because of its large direct wide band gap (~3.37 eV), high exciton
binding energy (~60 meV) and the most important, dependence of
mobility of charge carriers in ZnO hetero-structures, on the po-
tential barrier height at the interface governed by the mismatching
of the electronic structure [28e31]. A type-I hetero-structure,
wherein both kinds of charge carriers (electrons and holes)
participate in conduction phenomenon is considered as a suitable
junction for photodetection applications, whereas, a hetero-
structure of type-II having only one kind of charge carriers (either
electrons or holes) for electronic transport is best fitted for semi-
conductor lasers. However, a variety of hetero-structure materials
are used with ZnO as an active material for different applications
[24e30] but there is a dearth of data on the hetero-junction of Fe-
doped ZnO with ZnO for UV photodetection application. Therefore,
in the present investigation, we have fabricated the hetero-junction
of Fe-doped ZnO with ZnO and systematically analyzed for struc-
tural, morphological and optical conformations. A methodical
979
analysis of the valence and conduction band offsets has been done
through X-ray photoelectron spectroscopy and then the under-
standing of band alignment at the interface has been employed to
realize the mechanism of UV photodetection in the deposited metal
oxide thin films.
2. Experimental details
2.1. Deposition of thin films
A set of three samples, pristine ZnO, Fe-doped ZnO
(Zn0.98Fe0.02O) with 2 wt% doping of Fe and hetero-junction of
Zn0.98Fe0.02O with ZnO (Zn0.98Fe0.02O/ZnO) were grown on highly
clean glass substrates under the oxygen environment by pulsed
laser deposition (PLD) technique. A KrF Excimer Laser (l ¼ 248 nm)
with laser energy of ~220 mJ was used to ablate the material from
the target in the oxygen ambient environment maintained through
a constant flow of highly (>99.99%) pristine oxygen gas at a partial
pressure of ~1 mTorr. The base pressure of ~1.7  10
6 Torr was
attained using turbo-molecular pump backed with rotary pump
before all the depositions. Prior to deposition, the targets of pristine
ZnO and Fe (2 wt%)-doped ZnO (Zn0.98Fe0.02O) were prepared by
the physical grinding (solid state reaction) method followed by
sintering at ~1150  C for 16 h. The substrates were ultrasonically
cleaned with acetone and methanol repeatedly and finally dried
with nitrogen gas. For all the depositions, the substrate were kept at
a distance of 5 cm from the target and maintained at a temperature
of 450  C.
2.2. Characterization of deposited thin films
The thicknesses of the deposited films were measured using a
surface profilometer (Dektak-150, Veeco, USA) and found to be
~200, 200 and 205 nm (5 þ 200 nm) for the pristine ZnO, for Fe-
doped ZnO (Zn0.98Fe0.02O) single layer and Fe-doped ZnO and
ZnO (Zn0.98Fe0.02O/ZnO) hetero-junction, respectively. The struc-
tural properties of deposited films were analyzed under X-ray
diffractometer, (D8 Discover Advance, ASX-Bruker made), whereas,
the optical properties were examined using UVeViseNIR spectro-
photometer (Varian Cary-5000, Netherlands). The surface
morphology of the deposited films was analyzed using an atomic
force microscope (AFM) (Model No. Nanoscope - III, Digital In-
strument). The elemental analysis of the deposited films was car-
ried out using X-ray photoelectron spectroscopy (XPS) using an
Omicron energy analyzer with a monochromatic Al Ka (1486.6 eV)
X-ray source, whereas, the valence band spectra of the deposited
films were obtained using He-II source (Energy: 40 eV) photoelec-
tron beam at Indus I synchrotron radiation source in an ultra-high
vacuum (~10
9 torr). To negate the effect of surface contamination,
all the samples were sputter cleaned using 5 keV Arþ ion sputtering
system embedded with XPS instrument. The UV photodetection
performance of the deposited films was analyzed under UV light of
wavelength ~365 nm at a fixed intensity of ~3.3 mW/cm2. The
photodetection measurements were carried out in parallel elec-
trode geometry with active surface area of 0.15 cm2, where two
parallel silver electrodes were made on the film surface and illu-
minated with a UV source. The change in electric current on illu-
mination was measured using Keithley 2410 source measure unit
(SMU) interface with personal computer through KUSB 488.2.
3. Results and discussion
3.1. Morphological and structural studies
Surface morphology of the deposited films has been analyzed
980 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990
under AFM studies (Fig. 1). AFM images of the deposited films shows
almost uniform distribution of small size particles/agglomerates
throughout the film surface. The grain size for the pristine ZnO is
found to be in the range of ~50e100 nm, while, in case of
Zn0.98Fe0.02O, the grain size is significantly reduced to less than
20 nm, this might be due to catalytic effect and difference in ionic
radii of Zn and Fe. In contrast to this, the particle/grain size (~50 nm)
for Zn0.98Fe0.02O/ZnO hetero-junction film is quite uniform and
lying between the pristine ZnO and Zn0.98Fe0.02O thin films. The
average surface roughness of the deposited films has also been
measured from the AFM micrographs and found to be 1.527, 2.958
and 2.227 nm for pristine ZnO, Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO
hetero-junction thin films, respectively. The higher roughness value
of the samples having lower grain size may be due to presence of
large number of ridges and trenches and increase in the porosity of
the samples as observed from the AFM images [32].
Fig. 2 shows the X-ray diffraction patterns of pristine ZnO,
Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO hetero-junction thin films,
perusal of data presented in Fig. 2, some well define reflections at
~30.12 , 33.42 , 46.38 and 77.88 corresponding the (hkl) plane
(100), (002), (102) and (004) planes of ZnO, respectively have been
observed. This suggests the polycrystalline nature of the deposited
films in wurtzite crystal symmetry, while, the dominance of (002)
plane located around 33.42 over the other (hkl) planes in all the
samples suggests the orientation of crystal structures of ZnO along
c-axis [24,33,34]. It has been noted that no extra peak correspond-
ing to Fe or Fe2O3 in the doped Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO
hetero-junction films is observed, thereby suggesting substitution
Fig. 1. AFM images of (a) Pristine ZnO, (b) Zn0.98Fe0.02O and (c) Zn0.98Fe0.02O/ZnO thin films.
of Zn2þ by Fe2þ ions on the lattice or interstitial sites of ZnO and
negate the existence of distinct phase of Fe like FeO or Fe2O3, etc.
Fig. 2b shows a slight shift in the peak position for the Zn0.98Fe0.02O
film towards low diffraction angle and an slight upward shift in case
of Zn0.98Fe0.02O/ZnO hetero-junction thin film that could be attrib-
uted to the substitutional effect of Zn2þ by Fe3þ ions which persuade
the lattice mismatching in wurtzite structure of ZnO because of
different ionic radii of Fe2þ (0.64 Å) and Zn2þ (0.74 Å) [33]. Due to
this a decrease in F bond length between Zn-O and Fe-O along the
orientation c-axis and to the accrual of residual stress in the plane of
the film takes place. Furthermore, it is observed that the full width at
half maximum (FWHM) also decreases with Fe doping and hetero-
structure formation, suggesting the increase in crystallite size as
compared to pristine ZnO film. The crystallite size in the present
samples was calculated by using standard Scherrer's formula given
by
0:91l
D¼ (1)
b cos q
where, b is the full width at half maximum of (002) peak, q is
diffraction angle and l is the wavelength of x-ray source
(CuKa ¼ 1.54 Å). The values of crystallite size for pristine ZnO,
Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO hetero-junction are observed
to be 10.1, 13.5 and 10.7 nm, respectively. The crystallite size is
found to increase with the incorporation Fe impurity or the for-
mation of hetero-structural thin films because of the replacement
of Zn2þ ions by Fe3þ ion or interfacing junction effect, which leads
 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990 981

Fig. 2. (a) X-ray diffraction patterns and (b) magnified view of (002) plane of ZnO, Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO hetero-junction thin films.

to strain in the crystal lattice and may affect the device perfor- optical behavior of the films suggests direct band to band transition
mance [35e39]. Therefore, the micro-strain (ε) commenced by Fe3þ and the absorption band energy can be calculated using Mott and
ions was calculated using the formula: Davis model [42].

b cos q
n
ε¼ (2) B hn
Eg1
4 a¼ (3)
hn
The values of the micro-strain observed in the deposited films
have been tabulated in Table 1 and observed that the micro-strain where, a is the absorption coefficient, hv is the incident photon
in films decrease with the replacement of Zn2þ ions by Fe3þ ions in energy, B is the proportionality constant related with the materials
ZnO crystal lattice. properties, Eg1 is the optical band gap and power index n can have
The dislocation density (d ¼ 1/D2), which is defined as the length values 1/2, 3/2, and 2 for the direct band gap, the direct forbidden
of dislocation lines per unit volume, also found to decrease with Fe- gap and indirect transitions, respectively. The experimental data of
doping and hetero-structure formations (Table 1), whereas, the absorption coefficient has been fitted with Mott and Davis relation
lattice parameter (c ¼ l/sin (q)) for the present deposited thin films (Equation (3)). The best fit has been observed for r ¼ 0.5, thereby
found to increase from 5.3586 (pristine ZnO) to 5.3995 Å indicating occurrence of direct allowed transitions in the deposited
(Zn0.98Fe0.02O) with Fe doping, which an usual effect accreted due thin films. The values of optical band gap energy (Eg1) and goodness
to different ionic radii of Zn2þ (0.74 Å) and Fe3þ (0.62 Å). of fit parameters (R2 and c2) obtained from fitting has been listed in
Table 2. Keeping in view, the shape of optical observation spectra
3.2. Optical absorption (UVeViseNIR) spectroscopy and high exciton binding energy (60 meV) of ZnO, the optical ab-
sorption spectra of deposited thin films have been analyzed in the
Optical properties of the deposited films have been studied light of Hydrogenic Excitonic Model (HEM), which provides an
using UVeVis spectroscopy techniques in the wavelength range of explicit understanding of the optical absorption via bound and
250e700 nm. The optical transmission of all the films has been continuum excitons. The absorption coefficient (a) introduced by
presented in Fig. 3, it has been observed that prepared films have Elliot and Washington for Hydrogenic excitons is given as [43e48].
more than 65% transparency in visible region, having a sharp ab- (
X∞ 
sorption edge at around 370 nm. Among presently studied thin C0 R1=2 2R Gm 1 p
films the Fe-doped thin film shows highest transparency in visible aðEÞ ¼ þ
E m¼1
m3 ðE
Em Þ2 þ t2m 2 2
region. The increase in optical transparency with Fe doping can be   X ∞
attributed to increase in optical band gap via the BursteineMoss Zu
Eg R tc
þ arctan
3 2
effect. Instead of increasing the carrier density, Fe doping results tc m¼1
m ðE
Em Þ þ tc
2
to the filling up of the energy level just below the conduction band
þ )
which blocks the charge carriers in prepared thin films and causes a p sinh 2u
þ

 (4)
shift into the absorption band edge called the B-M shift [40]. 2 cosh 2uþ
cos 2u

A similar behavior was observed by Yousif in Fe doped ZnO thin
film prepared by Spray Pyrolysis technique [41]. The observed where,

Table 1
Structural parameters associated with pristine ZnO, Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO hetero-junction thin films.

Sample Name Lattice parameters ‘C’ (Ǻ) Crystallite size ‘D’ (nm) Dislocation density ‘d’ (lines/m2) Strain ‘ε’ Mismatch strain
15
3
Pristine ZnO 5.3586 10.1 9.8030  10 3.69  10 0.967
Zn0.98Fe0.02O 5.3995 13.5 5.4870  1015 3.27  10
3 1.007
Zn0.98Fe0.02O/ZnO 5.3524 10.7 8.7344  1015 2.59  10
3 0.998
982 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990

Fig. 3. (a) Transmission spectra of ZnO, Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO hetero-junction thin films, (b) fitting of absorption coefficient (a) using Mott and Davis's model (MDM)
with equation (3) and (c) fitting of absorption coefficient (a) using Hydrogenic excitonic model (HEM) with equation (4) for ZnO, Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO hetero-junction
thin films.

h i
 1=2 "
E
E 2 þ t2 1=2 H
E
E #
1=2
R g2 c g2
Table 2 u± ¼ p ; Em
Values of optical energy band gap (Eg1), Best fit parameter (aR2) and Reduced chi
2 ðE
Em Þ2 þ t2c
square (aХ 2) obtained from the fitting of experimental data of absorption coefficient R .
spectrum with Mott and Davis model (Equation (3)) and values of optical energy ¼ Eg2
2 &tm ¼ tc
ðtc
t1 Þ m2 ; m ¼ 1; 2; 3:
band gap (Eg2), excitonic binding energy (R), line widths for m ¼ 1 state (t1), line m
width of continuum (tc) and absorption strength (Co), Best fit parameter (R2) and
Reduced chi square (c2) obtained from the fitting of experimental data of absorption where Co is absorption strength parameter, Eg2 is optical band gap
coefficient spectrum with Hydrogenic excitonic model (Equation (4)) for ZnO, energy, E is incident photon energy, R is excitonic binding energy,
Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO films. and t1 and tc are line widths of m ¼ 1 state and of continuum,
Sample Name Parameters ZnO Zn0.98Fe0.02O Zn0.98Fe0.02O/ZnO respectively.
The experimental data of a has been fitted with Hydrogenic
Eg1 (eV) (MDM) 3.213 3.234 3.243
a 2
R 0.894 0.855 0.882 excitonic model (Equation (4)) taking excitonic Binding energy (R)
a 2
c 1.28  1012 8.065  1013 1.302  1014 equal to 60 meV and keeping all other parameter free (Fig. 3c). The
Eg2 (eV) (HEM) 3.340 3.351 3.361 values of parameters Eg2, t1, tc, Co and goodness of fit parameters
R (eV) 0.06 0.06 0.06 (R2 and c2) obtained from the fitting are listed in Table 2. The values
t1 (eV) 0.443 0.475 0.536
of fitting parameters t1, tc and Co are in good agreement with the
tc (eV) 0.058 0.086 0.065
Co (eV1/2/cm) 5.337  107 4.566  107 6.477  107 values of these parameters reported in literature values [46,47].
b 2
R 0.981 0.950 0.987 Perusal of the data of best fit parameters obtained from MDM and
b 2
c 2.238  1011 4.018  1011 2.074  1011 HEM presented in Table 2, it has been observed that Hydrogenic
excitons model fits the studied experimental data of a more
 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990
appropriately than MDM. However the values of optical band gap
energy obtained from both models show similar trend and more or
less same values. The values of optical band gap obtained from
fitting of HEM are almost equal to the standard reported values in
literature for ZnO [31e33]. The optical band gap in the presently
studied thin films increases with Fe doping and it further increase
in hetero-structures thin films. This increase in band gap may be
attributed to B-M shift [39], wherein, when ZnO film is doped with
Fe, the Zn2þ ions may replace by Fe3þ ions at substitutional sites,
which results in an increase in free carrier concentration, resulting
in low energy transition as can be seen from Fig. 3a. This will cause
to shift the Fermi level in conduction band and may responsible for
broadening of optical bandgap.
3.3. Elemental and chemical bonding analysis by XPS
For the elemental analysis or the better understanding of
chemical composition of the deposited films, X-ray photoelectron
spectroscopy investigations have been carried out on the deposited
films. Fig. 4a shows wide range survey scan of Zn0.98Fe0.02O film
consisting various peaks corresponding to different configurations
of ZnO including Zn 3d, 3p, 3s and 2p states, along with a doublet of
Fe located around 710.6 and 724.1 eV binding energy for Fe 2p3/2
and 2p1/2, respectively. Apart from the bands associated with Zn, an
intense feature of oxygen is also observed at ~533 eV, suggesting
the formation of chemical structure of ZnO. The strong spin-orbit
coupling in ZnO resulted into the splitting of Zn 2p energy level
into two components located at 1022.6 and 1045.6 eV, separated by
an energy gap of 23 eV (inset Fig. 4a). The energy difference of 23 eV
between Zn 2p3/2 and 2p1/2 doublet, confirms the deposition of
quality ZnO film [48].
To understand the effect of Fe doping and hetero-structure
formation on the spin orbit coupling or on the core level spectra
of Zn, the XPS core level spectra of Zn 2p for the pristine ZnO,
Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO of thin films have been pre-
sented in Fig. 4b-c. It has been observed that the peak positions of
Zn 2p doublet shift towards lower binding energy with Fe doping as
well as with hetero-structure formation. The 2p3/2 level of ZnO is
found to shift from 1022.5 to 1022.06 eV (i.e. by 0.44 eV) with Fe
doping, while this shifting is of 0.21 eV for Zn0.98Fe0.02O/ZnO
hetero-structured thin film. Furthermore, the energy difference
between Zn 2p3/2 and 2p1/2 also increases from 23.0 to 23.12 eV
with Fe doping and hetero-structure formation i.e. a widening of
0.12 eV for both the Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO hetero-
structured thin films via the strong spin-orbital coupling.
To investigate the different kinds of bonding states of zinc with
oxygen in pristine ZnO thin films, and with iron or iron with oxygen
in Zn0.98Fe0.02O thin film. Fe can be generally found in two oxida-
tion states Fe2þ and Fe3þ [49], but XRD studies discard the presence
of distinct phase of iron in FeO or Fe2O3 i.e. Fe2þ or Fe3þ ions, rather
these ions just produced the substitution effect in the present films.
Therefore, Fe can be found in co-bonding states with Zn and O like
Fe-O-Zn. Zn can also be found in unbounded states at its interstitial
positions or through oxygen vacancies due to oxygen deficiency in
the crystal structure. Therefore, to resolve different components of
bonding states in the pristine ZnO and Fe-doped films are decon-
voluted into different component using the combination of
Gaussian-Lorentzian distribution functions after a subtraction of
background from the spectra by linear-method, as shown in Fig. 5a-
c. The Zn 2p3/2 spectrum of pristine ZnO thin films is deconvoluted
into two components associated with the metallic Zn (Znm) or the
surface adsorbed oxygen/hydroxyl groups located at 1022.05 eV
and bonding state of Zn with O (Zn-O) positioned at 1022.97 eV,
whereas, the Zn 2p3/2 core level spectrum of Fe0.02Zn0.98O is
deconvoluted into three components which are attributed to the
983
metallic Zn (Znm) or free surface oxygen located at 1021.24 eV,
bonding state of Zn and Fe with O (Fe-O Zn) peaked at 1022.08 eV
and the chemical bonding between Zn and O (Zn-O) positioned at
1022.96 eV. The Zn 2p3/2 spectrum of hetero-structured
(Fe0.02Zn0.98O/ZnO) thin film has also been deconvoluted into
three components viz. a viz. The metallic Zn (Znm) or chemisorbed
oxygen or water molecules/OH species, bonding state of Zn and Fe
with O (Fe-O Zn) and the chemical bonding between Zn and O (Zn-
O) located at 1021.52, 1022.42 and 1023.48 eV, respectively. The
bonding states of Fe-doped ZnO thin films can be corroborated with
different kinds of doping in ZnO matrix [50e54]. The peak posi-
tions, area under the curves and the FWHM values for different
components have been tabulated in Table 3.
Fig. 5(def) shows the deconvoluted core level (CL) spectra of
oxygen (1s) for the deposited thin films. The core level spectra of
oxygen (1s) has large asymmetry towards higher binding energy
side for all the films suggesting the presence of O in different
bonding states with Zn or co-bonding with Zn and Fe in
Fe0.02Zn0.98O and Fe0.02Zn0.98O/ZnO thin films. Furthermore, the
peak position for core level spectrum of oxygen (1s) is found to shift
from 530.82 to 530.75 eV (by 0.07 eV) with Fe-doping and
530.82e530.92 eV (by 0.10 eV) through hetero-structural forma-
tion. However, there is only a slight shift in the peak positions via
structural transformation, but because of the sensitiveness of XPS
measurements, this slight shift is sufficient to make a judgment on
the change in bonding states through incorporation of some foreign
impurities (Fe3þ ions) at the interstitial or substitutional sites of Zn
causing to lattice structure defect in ZnO network. The incorpora-
tion of Fe3þ in ZnO matrix leads to new bonding states of Zn with
oxygen and Fe. Therefore, the core level oxygen spectrum of pris-
tine ZnO thin film is deconvoluted into two components while for
Fe0.02Zn0.98O, and Fe0.02Zn0.98O/ZnO thin films into three compo-
nents. The peaks located at 532.65 and 530.86 eV in pristine ZnO
thin films are attributed to the stoichiometric bonding states of O
with Zn (Zn-O), and chemisorbed oxygen molecules which can be
found into different molecular bonding states like CO, CO3, OH or
H2O at the film surface or free ionic forms (O2, O
, or O
2 ) adsorbed
at ZnO surface, respectively [51e55]. The component at higher
binding energy side can be due to non-stoichiometric ZnOx (OH)y
form of ZnO. While in case of Fe0.02Zn0.98O and Fe0.02Zn0.98O/ZnO
thin films an additional component arises from the bonding be-
tween Zn, Fe and O (Fe-O-Zn) located at 530.90 and 531.20 eV,
respectively. The peak positions for different components such as
the stoichiometric bonding states of O with Zn (Zn-O), chemical
bonding between Zn, Fe and O (Fe-O-Zn) and chemisorptions of
oxygen or non-stoichiometric ZnOx (OH)y have been recorded into
Table 3 along with corresponding area under curves and FWHM
values.
3.4. Valence and conduction band offsets measurements
The knowledge of charge carrier confinement phenomena in the
doped and hetero-structure thin films plays a crucial role in un-
derstanding type of charge carrier participating in conduction
process for their plausible applicability in different quantum well
devices including light emitting diodes, photodetector, and
advanced spintronic devices, etc. The charge carrier confinement
process can be easily understood through valence band spectros-
copy because of its high sensitivity towards surface adsorbates like
chemisorbed oxygen molecules/ions and its usefulness in under-
standing the type of hybridization of the molecules. Moreover, a
shift in valence band edge (valence band offset, VBO) and con-
duction band edge (conduction band offset, CBO) provide extensive
information about the conduction mechanism in the doped and
hetero-structured thin films. The degree of valence band offsets can
984 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990

Fig. 4. (a) General survey scan of Zn0.98Fe0.02O thin film (inset: magnified view of 2p spectrum of ZnO), XPS 2p core level spectra of (b) ZnO, (c) Zn0.98Fe0.02O and (d) Zn0.98Fe0.02O/
ZnO thin films.

be estimated by analyzing the core level and valence band spectra between the core level position of the Zn 2p3/2 in the ZnO and Fe 2p3/
of Zn in pristine ZnO, Fe0.02Zn0.98O and Fe0.02Zn0.98O/ZnO thin films ZnO
E ZnO Þ is the energy differ-
in the Zn0.98Fe0.02O/ZnO, and ðEZn2p
2 VBM
[26e30]. Therefore, the 2p3/2 core level spectrum of Zn is fitted ence between the core level of Zn 2p3/2 and valence band maximum
with Lorentzian distribution function after linear type base line (VBM) in ZnO film, whereas, ðEFe2p
0:98 Zn Fe0:02 O=ZnO Zn

EVBM
0:98 Fe0:02 O=ZnO
Þ is the
correction, for all the deposited thin films, as shown in Fig. 6(aec),
energy difference between the core level of Fe 2p3/2 and VBM in
whereas, the valance band maxima (VBM) has been estimated by
Zn0.98Fe0.02O/ZnO film. The estimated values for valence band off-
linear extrapolation of leading edge of valence band spectra as
sets for Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO thin films are 0.03 and
shown in Fig. 6(def) [30].
0.37 eV, respectively. The positive value of VBO for both the samples
The values of peak position and VBM for all the films are pre-
confirms the confinement of hole at the interface. The estimated
sented in Table 4 and observed that the peak position of 2p3/2 core
value of valence band offsets for Zn0.98Fe0.02O/ZnO hetero-junction
level of Zn and VBM undergo downward shifted with Fe-doping as
is well matched with the reported VBO values for different hetero-
well as with hetero-structure formation.
junctions of ZnO. The conduction band offset (DEC), in the
The valence band offsets (DEVBO) in the Zn0.98Fe0.02O and
Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO thin films has been measured
Zn0.98Fe0.02O/ZnO thin films has been calculated using well known
using the relation [24e28,34],
Kraut's relation [56].

ZnO Fe O=ZnO
  DECBO ¼ EZnO
g
Eg 0:98 0:02
DEVBO (7)
ZnO ZnO Zn0:98 Fe0:02 O=ZnO
DEVBO ¼ DECL
EZn2p
EVBM þ EFe2p
where, EZnO
g
ZnO
and Eg 0:98 0:02
Fe O=ZnO
are the band gap energies of the
Zn Fe0:02 O=ZnO

EVBM
0:98
(6) ZnO and Zn0.98Fe0.02O. The conduction band offsets Zn0.98Fe0.02O
and Zn0.98Fe0.02O/ZnO thin films are found to be
0.042 eV
ZnO
E 0:98 Zn Fe0:02 O=ZnO
where, DECL ¼ EZn2p Fe2p is the energy difference and
0.393 eV, respectively. The negative value of CBO for both the
 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990 985

Fig. 5. Deconvoluted ZnO core level (2p3/2) spectra of (a) ZnO, (b) Zn0.98Fe0.02O and (c) Zn0.98Fe0.02O/ZnO of thin films, deconvoluted oxygen core level (C1s) spectra of (d) ZnO, (e)
Zn0.98Fe0.02O, and (f) Zn0.98Fe0.02O/ZnO of thin films.

Table 3
Peak position, area under the curve and FWHM values of various components in pristine ZnO, Fe0.02Zn0.98O, Fe0.02Zn0.98O/ZnO thin films.

Sample Peak Assignment Peak position (eV) Area under the curve FWHM (eV)

ZnO Znm 1022.05 51354.98 1.36

Zn-O 1022.97 53538.88 1.67
Fe0.02Zn0.98O Znm 1021.24 27266.41 1.02
Fe-O-Zn 1022.08 49904.41 0.98
Zn-O 1022.96 30125.69 1.34
Fe0.02Zn0.98O/ZnO Znm 1021.52 29236.96 1.02
Fe-O-Zn 1022.42 43741.69 0.99
Zn-O 1023.48 22218.48 1.37
ZnO O
2 in ZnO 532.65 14096.61 2.73
Chemisorbed O2, O
, or O
2 530.86 19906.64 1.49
Fe0.02Zn0.98O O
2 in ZnO 530.31 6818.471 1.04
O2
in Fe-O-Zn 530.90 21056.69 1.42
Chemisorbed O2,O
, or O
2 532.20 14859.34 2.66
Fe0.02Zn0.98O/ZnO O
2 in ZnO 530.60 9893.31 1.26


O2 in Fe-O-Zn 531.20 9008.36 1.34
Chemisorbed O2, O
, or O
2 532.51 13979.48 2.65

samples suggest that the conduction will take place at lower energy
than that of pristine ZnO sample, which confirms a band alignment
of type II (straddling). Thus the valence and conduction band offsets
suggest the confinement of hole at interface and higher value of
valence band offset as compared to CBO suggesting that the charge
transport is majorly governed by the electrons [36,57].
The observed values of the DEv and DEc for Zn0.98Fe0.02O and
Zn0.98Fe0.02O/ZnO hetero-junction may depend on the depositions
conditions, kind of doping, strain induced by the incorporation of
foreign impurities, atomic re-arrangement and difference in the
electro-negativity of O2
ion towards other ions as compared to
Zn2þ ions. The small band offsets in the present samples could be
due to lattice mismatching and the strain induced by the doping of
Fe because of the different atomic size and oxidation state of Fe3þ as
compared to Zn2þ. The observed negative conduction band offsets
and positive valence band conduction values suggesting the up-
ward shifting of valence and downward shifting of conduction band
for both the Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO thin films as
shown in Fig. 7, which is the characteristic of type-II band align-
ment of semiconductor. The ratio of conduction band offset to
valence band offset (DEc/DEv) in Zn0.98Fe0.02O/ZnO is found to
be
1.062. The lower value of VBO as compared to CBO may be due
confinement of the holes at the interface and conduction phe-
nomenon mainly governed by electrons. The materials showing
conduction only one type of charge carriers may be useful for the
device application in selective photo-detectors [57].
986 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990

Fig. 6. XPS 2p3/2 core level spectra of (a) ZnO, (b) Zn0.98Fe0.02O and (c) Zn0.98Fe0.02O/ZnO hetero-junction thin films, VBM spectra for (d) ZnO, (e) Zn0.98Fe0.02O, and (f) Zn0.98Fe0.02O
thin films.

Table 4 3.5. UV photodetection behavior of pristine and Fe-doped ZnO thin

Peak positions of Zn core level and VBM values for pristine ZnO, Zn0.98Fe0.02O and films
Zn0.98Fe0.02O/ZnO hetero-junction thin films.

Sample Name Region Binding Energy (eV) Fig. 8(aec) shows the UV photoresponse of the pristine ZnO,
ZnO Zn:2p3/2 1022.47 Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO thin films recorded in UV light
VBM 3.00 of wavelength ~365 nm at a fixed intensity of ~3.3 mW/cm2 at a bias
Zn0.98Fe0.02O Zn:2p3/2 1022.04 voltage of ~0.01 V. The change in electric current has been
VBM 2.97
measured in dark as well as under UV illumination as a function of
Zn0.98Fe0.02O/ZnO Zn:2p3/2 1022.16
VBM 2.63
time. The films are allowed to expose for 90 s to acquire maximum
current and then allowed to recover for 100 s after switch off the
light. It is observed that the electric current in the deposited films
increases with UV exposure time via the generation of electron-
hole [hv / e
þ hþ] on exposing the film surface with UV light

Fig. 7. Band alignment diagram for ZnO, Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO thin films.
 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990
Fig. 8. UV photoresponse of (a) ZnO, (b) Zn0.98Fe0.02O (c) Zn0.98Fe0.02O/ZnO thin films, and (d) Schematic representation of upward band bending in metal oxides thin films via
electron trapping process through surface adsorbed oxygen molecules.
photons [34,55,58,59]. The photo-generated electrons may move to
the conduction band of the films and responsible for increase in
electrical current in UV light. The change in electric current is used
to calculate the photoresponse of the films using the formula,
Il
Id DI
Response ¼  100 ¼  100
Id Id
where, Id is the dark current and Il represents the current under UV
illumination. The photoresponses for the deposited films are found
to be ~25, 36 and 26% for the pristine ZnO, Zn0.98Fe0.02O and
Zn0.98Fe0.02O/ZnO thin films (Fig. 8a-c).
To check the repeatability of the films, three cycle of the pho-
toresponse are recorded and observed that all the films have
regenerative response which is required for practical photodetec-
tors. The transient photocurrent of the metal oxide thin films is
generally governed by the surface adsorbed oxygen molecules,
which pulled out the electron from the conduction band of the
metal oxide to form oxygen ions (O
2

2 or O , etc.) [O2 (ads) þe-

(10)
4O2 (ads)]. This will result into the decrease in charge carrier
concentration and responsible for high resistivity of metal oxide
films. The surface adsorbed oxygen molecules create a space
charged region at the grains and grain boundaries at the film sur-
face and are responsible for upward band bending or creation of a
987
potential barrier of height FB (Fig. 8d). The length of band bending
equal to the length of space charge regions (FB ¼ eVs), Vs is surface
potential and the electric current in the film is given by
Refs. [60,61].

eV 
f
I ¼ Io e
kT ¼ Io e
kT
S B
(9)
(8)
On the illumination of these films, the electron-hole pairs are
generated on the film surface. The photo-generated holes interact
with the O

þ
2 ions on the film surface {O2 (ads)þh /O2 (gas)},
whereas, electrons are either trapped by the re-adsorbed oxygen
molecules or collected at the electrodes and responsible for
enhanced photocurrent via the decrease in potential barrier height
and the width of space charged region at the grains and grain
boundaries. Thus the photoresponse in the present films is gov-
erned by the change in potential barrier height or degree of band
bending in UV light [62e65], as


ef 
Response ¼ eð kT Þ ¼ e kT

eDn B
The highest photoresponse of Zn0.98Fe0.02O thin film as
compared to pristine ZnO and Zn0.98Fe0.02O/ZnO hetero-structured
thin films can be attributed to the enhanced surface to volume ratio
and presence of large number of surface active sites or surface
988 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990
structures. The incorporation of Fe3þ ions into ZnO network may
also help in increasing the mobility of charge carriers and better
photoresponse. Moreover, the enhanced photoconductivity in Fe-
doped ZnO film can be attributed to the improved optical trans-
parency in visible reason and Fe-doping effects. Doping of Fe3þ ions
in ZnO films may act as cationic dopants which make easy for the
electrons to transport in the conduction band. On UV illumination,
the charge carriers trapped in the defect states introduced by the
dopants can be easily excited into the conduction band and hence,
responsible for enhanced photoconductivity in doped state.
The device performance and detection limit of a photodetector
are generally analyzed in terms of responsivity (Rl) and detectivity,
where, responsivity is defined as the number of photo-generated
charge carriers per incident number of photons i.e. it is the mea-
surement of sensitivity of a device towards the illumination in-
tensity [66e70]. Mathematically, it can be expressed as
Jp DI
Rl ¼ ¼ (11)
pd pd A
where, Jp is the photo-current density and Pd is the illumination
intensity, A is the sample area illuminated. The responsivity in the
present deposited films has been calculated using eq. (11) at a fixed
illumination intensity of 3.3 mW/cm2 and the responsivity values
for the pristine ZnO, Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO thin films
are found to be 1.56, 2.17 and 1.86 mA/W, respectively. Ning et al.
[71] observed a decrease in responsivity of the ZnO nanofibers
prepared by electrospinning method from 1.28 to 0.86 mA/cm2
with increase in illumination intensities from 0.5 to 2.8 mW/cm2,
whereas, Zhao et al. [72] were studied UV photodetection behavior
of ZnO-Ga2O3 heterostructures and observed a variation in
responsivity of the heterostructure with illuminating wavelength.
A maximum responsivity of 9.7 mW/cm2 is observed on the illu-
mination with UV light of wavelength 251 nm. The observed
responsivity in the present thin films is comparable to the reported
literature values for different metal oxide UV photodetectors.
The device performance of a photodetector can also be esti-
mated in terms of detectivity, which is defined as ability of a
photodetector to detect weak optical signal i.e. it is measurement of
high signal to noise ratio [68e70]. Mathematically, it can be rep-
resented as,
R 3.34  10
4 S/cm for the pristine ZnO, Zn0.98Fe0.02O and
D ¼ pffiffiffil
2eJd
where, e is the electronic charge and Jd is the dark current density.
The detectivity values for present deposited pristine ZnO,
Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO thin films are found to be
4.29  109, 5.48  109 and 6.45  109 cmHz1/2/W, respectively. The
parameters associated with the device performance in the present
study are tabulated in Table 5.
The observed detectivity of present thin films is comparable to
the reported detectivity values for ZnO films in its pristine and
doped form, suggesting excellent device ability to detect a much
weaker UV signal [68,70,73]. For example, in a study on ZnO
nanoflake Boruah and Misra [74] observed a detectivity value of
Table 5
Device performance parameters for the deposited films.
Sample Name Response (%) Rise time (s)
ZnO 25 47
Zn0.98Fe0.02O 36 77
Zn0.98Fe0.02O/ZnO 26 73
5.48  1010 cmHz1/2/W at a power density of 3 mW/cm2. Further-
more, to correlate the device performance parameters (responsiv-
ity and detectivity) with the reported literature, responsivity and
detectivity values observed for different samples prepared by
different techniques are provided in Table 6.
The number of electron-hole pair generated per incident photon
for a given wavelength (l) of illuminating light is generally termed
as photon to electron conversion efficiency, so called external
quantum efficiency (EQE). The external quantum efficiency or the
light harvesting efficiency is widely used as a parameter of device
performance. The external quantum efficiency can be estimated
using formula [68,69].
Jp hc Rl hc
EQE ¼ ¼ (13)
pd el el
The values of external quantum efficiency for pristine ZnO,
Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO thin films are found to be
~5.31  106, 7.38  106 and 6.35  106, respectively. The observed
value of the EQE is better than that for Individual Single-Crystalline
Zn2GeO4 Nanowires by Zhou et al. [70]. The obtained values of EQE
are well corroborated with the reported literature values for ZnO
based photodetectors. Thus, the quite high values of the parameters
such as responsivity, detectivity and external quantum efficiency
associated with the device performance suggest the ability of these
devices to be used for device fabrication for practical applications.
3.6. Electrical properties
ZnO thin films are always remained the centre of attention for
their high optical transparency along with high conductivity for
optoelectronic applications. Therefore, the electrical properties of
the present films have been investigated through electrical mea-
surements performed by two probe surface electrode method,
where two parallel silver electrodes are made with conducting
silver paste on the film surface. I-V characteristics of the pristine
ZnO, Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO thin films have been
recorded in parallel electrode geometry and shown in Fig. 9. I-V
characteristics for all the samples have linear variation of voltages
at different applied currents, suggesting the ohmic nature of the
contacts. The value of the surface conductivity measured from
these characteristics are found to be 6.61  10
2, 1.33  10
4, and
(12) Zn0.98Fe0.02O/ZnO thin films, respectively. The electrical conduc-
tivity of the ZnO thin films found to be decrease with Fe-doping.
4. Conclusions
The structural and morphological properties of the deposited
films have been investigated through XRD and AFM studies. AFM
studies revealed that the grain size decreases with Fe-doping may
be due to catalytic effect of Fe, whereas, XRD studies suggesting the
polycrystalline nature of all the films. All the films having wurtzite
crystal structure of ZnO orientated about c-axis. UVeVis spectros-
copy studies revealed the high transparency of all the films and a
decrease in optical band gap with Fe-doping. XPS studies
Decay time (s) EQE Responsivity mA/W Detectivity cmHz1/2/W
 106
90 5.31 1.56 4.29  109,
63 7.38 2.17 5.48  109
42 6.35 1.86 6.45  109
 K. Singh et al. / Journal of Alloys and Compounds 768 (2018) 978e990 989

Table 6
Comparison of device performance parameters for ZnO thin films with reported literature.

Sample Technique Wavelength nm Responsivity mA/W Detectivity cm Hz1/2 W
1 Power density mW/cm2 Ref.

ZnO film PLD 365 21.65 2 [16]

PANI/MgZnO OCVD 250 0.160 1.5  1011 [26]
ZnO Nanofiber Electro- spinning 260 0.86 e 2.8 [68]
ZnO/Ga2O3 CVD 251 9.7 6.29  1012 [69]
Co-ZnO nanoflakes RF-sputtering 378 3 5 [70]
ZnO nanoflakes CVD 365 2.65 5.25  1010 3 [71]
ZnO Film PLD 365 2.17 5.48  109 3.3 This work

coating, J. Alloys Compd. 695 (2017) 3753e3759.

Fig. 9. IeV characteristics of the pristine ZnO, Zn0.98Fe0.02O and Zn0.98Fe0.02O/ZnO thin
films.
suggesting the presence of ZnO in different bonding states in
pristine as well as in doped thin film forms. The valence and con-
duction band offsets in the hetero-structure thin film have been
estimated by XPS and VBS studies. The valence band shows an
upward shift with 0.37 eV, whereas, a downward shifting is
observed in the conduction band of
0.393 eV for the Zn0.98Fe0.02O/
ZnO thin film, suggesting the type-II band alignment for the film.
The ratio of conduction band offset to the valence band offset is
about
1.062. The photoconduction behavior of the deposited films
have been investigated under UV light at a fixed intensity of
3.3 mW/cm2, and observed a reasonable photoresponse of the
deposited films for with excellent external quantum efficiencies.
Acknowledgements
One of the authors (K. Singh) is grateful to UGCeBSR for
providing the senior research fellowship. The authors are grateful
to Professor Vinay Gupta, Department of Physics and Astrophysics,
University of Delhi, Delhi, for providing the PLD facility for the
growth of the films. The authors are also thankful to the Director of
the UGC-DAE Consortium for Scientific Research, for providing XPS
and AFM characterization facilities for these samples.
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