Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-020-04046-7

Characterization of MgO thin film prepared by spray pyrolysis

technique using perfume atomizer
S. Visweswaran1   · R. Venkatachalapathy1 · M. Haris2 · R. Murugesan3

Received: 2 March 2020 / Accepted: 18 July 2020

© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
Transparent conducting magnesium oxide (MgO) thin films are obtained by pyrolytic decomposition of magnesium acetate
in a mixture of ethanol and distilled water on to a glass substrate using perfume atomizer. The substrate temperature (Ts) is
maintained at 300 °C, 350 °C, 400 °C, and 450 °C for depositing the films and annealed at 450 °C for 4 h. Then the samples
were characterized by X-ray diffraction, field emission scanning electron microscope, atomic force microscope, UV–Vis spec-
troscopy, photoluminescence analyzer, and Raman spectrophotometer for identifying its structure, morphology, topography,
bandgap and defect states. The XRD result demonstrates the cubic, polycrystalline nature with (2 0 0) preferred orientation.
The presence of ­MgO2 phase along (2 2 2) plane increases with substrate temperature is noticed. From the SEM monograph,
the clusters of spherical grains are observed for all the films and the columnar growth of the MgO film is observed from the
AFM topographical image. The surface roughness tends to increase with substrate temperature. The MgO thin films possess
two absorption bands and two optical bandgaps. The transmittance of 70% is obtained for MgO film which could be used
for optoelectronic device and protective coating applications. The blue and green emission bands are identified from the PL
spectrum. The defects in the film are responsible for linear I–V characteristic and the large forward current value implies
higher efficiency for solar cell applications.

1 Introduction hardness (5000 MPa), and elevated melting temperature

Magnesium oxide (MgO) thin films have a significant role
in optoelectronic devices, light-emitting diodes, piezoelec-
tric devices, photodetectors, sensors and solar cells, plasma
panels, smart and wearable devices, electrochromic device,
wastewater treatment, drug delivery, and health care industry
[1–8]. MgO is an ionic solid known as halite, in cubic rock
salt form. It consists of two oxygen anion and metal cation
interpenetrating the FCC sublattice [9]. Transparent con-
ducting oxide (TCO) having high optical transparency and
electrical conductivity is the advantage of MgO thin film.
Its properties include wide bandgap energy (7.8 eV), die-
lectric constant (6.8), thermal conductivity (42 ­Wm−1K−1),
* S. Visweswaran
visudharan@gmail.com
1
Department of Physics, Annamalai University,
Annamalainagar, Chidambaram 608 002, India
2
Department of Physics, Karunya Institute of Technology
and Sciences, Coimbatore 641 114, India
3
Department of Physics, Thiru Kolanjiappar Government Arts
College, Vridhachalam 606001, India
[10]. In general, three types of vacancies are found for MgO
identified as Fs, Fs+, F2+
s (color centers) depending on the
number of electrons trapped found from PL analysis [11].
Due to its significant variation in size and morphological
dimensions or structures nanowires [12], microtubes [13],
nanorods [14], sheets, flakes, nanoflowers [15], needles
are obtained from various deposition methods such as vac-
uum arc diffusion [16], spin-coating [12] dip-coating, dc/
rf magnetron sputtering [17–19], e-beam evaporation [20],
spray pyrolysis [21], thermal decomposition [22], neutron
irradiation [23], SILAR [24], pulsed laser deposition [25],
hydrothermal [26]. Valanarasu et al. [27], investigated on
MgO thin film by spin-coating technique. The transmittance
increases as the function of annealing times and it shows sur-
face plasmon resonance. The optical band gap lies between
3.81 and 3.92 eV. And it is a potential candidate for semi-
conducting device applications. Lee et al. [28], expressed
secondary electron emission (SEE) of undoped and tran-
sition metal-doped MgO. Doping transition metal to MgO
induces local stress due to the expansion and contraction of
bond length to adjacent atoms. The bond length of Fe–O is
similar to Mg–O. Higher the defect, higher is SEE which

13
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could be used as a display in plasma panel devices. The
hybrid thin films of ZnO and MgO on glass substrate are
employed through the spin-coat technique which can be used
in the optoelectronic industry. The thermal annealing of thin
film causes some cracks identified from SEM monographs
which are due to the stress in the film as reported by Balta
et al. [29]. The spray-deposited MgO thin film is used as
an ammonia gas sensor. This property at room temperature
resulted in better response as the concentration increases
were reported by Nisatharaju et al. [30]. Ezhil raj et al. [21],
studied the effect of various precursors for the deposition of
MgO thin film. The intensity of preferred orientation along
(2 0 0) and the crystallite size is high for acetate precursor
compared with nitrate and chloride precursor. Likewise, the
acetate precursor has high transmittance of above 80% and
the optical band gap of 5.25 eV. The influence of substrate
temperature on spray-deposited MgO thin film was investi-
gated. The increase in substrate temperature results in tex-
tured growth of (111) plane and lattice constant [31]. The
computation reports on the bandgap of MgO compounds
is found to be about 3.5–7.6 eV [32]. Suárez-Campos et al.
[33] showed the transformation of Mg(OH) 2 thin film to
MgO thin film by thermal treatment. The as-deposited thin
film reveals the presence of Mg(OH)2 reflection planes and
as the temperature increases, Mg(OH)2 phase is completely
transformed to MgO at 500 °C. Likewise, interconnected
nanowall-like morphology is observed for MgO thin film
and their corresponding O/Mg composition of 0.7 is attrib-
uted to oxygen vacancy. The bandgap value of the MgO thin
film is 5.10 eV. Guney et al. [34] grown Cd-doped MgO thin
film by SILAR technique and their structural, morphologi-
cal, and optical properties were studied. In addition to MgO
planes, there exist planes of CdO. As the doping concentra-
tion increases, the transmittance is decreased. The PL emis-
sions of undoped and doped MgO film lie in visible region
which could be used in optic display devices. The MgO and
Mg-doped ZnO thin film is grown on GaN and (0 0 1) ori-
ented α-Al2O3 substrates by atomic layer deposition. The
textural growth of thin film strongly depends on the substrate
used [35]. Khanfar et al. [3] reported the performance of Au/
MgO/Ni photovoltaic device. The device efficiency depends
on the bandgap of the MgO layer. The device records a high
quantum efficiency of 66%, the responsivity of 0.179 A/W,
and an open-circuit voltage of 0.12 V for an incident UV
photon at 2.2 μW optical power. The current density of the
device is 3.9 μA/cm2, is low compared to organic photovol-
taic cells. The films with preferred orientation along (2 0 0)
and (2 2 0) planes for MgO and Al-doped MgO films are
fabricated by sol–gel spin-coating technique. The crystallite
size increases as the Al doping concentration increases. The
strong absorption edge around 300 nm for all the films and
the transmittance decreased with an increase in Al doping.
As the Al increases, the morphology of grains changed from
13
Journal of Materials Science: Materials in Electronics
granular structure to spherical structure [36]. In the present
paper, perfume atomizer spray was employed to deposit
MgO thin film and its structural, morphological, optical,
and electrical properties are presented.
2 Experimental description
MgO thin films were deposited on glass substrates
by spray pyrolysis using perfume atomizer described
elsewhere [37–39]. Magnesium acetate tetrahydrate
­[MgC4H6O4∙4H2O] was used as a precursor. Ethanol and
deionized water are used as a solvent. Initially before the
film deposition, the glass substrates were scrubbed with
soap solution and then with acetone, HCl, and DI water and
dried. The spray solution was prepared by taking 0.1 M of
­MgC4H6O4∙4H2O in the mixture of ethanol and deionized
water. The solution was then homogenized ultrasonically.
The glass substrates were placed on a hotplate fitted with
temperature controller and a thermocouple is maintained at
300 °C, 35º0C, 400 °C, and 450 °C. The deposited samples
were annealed in air at 450 °C for 4 h in a muffle furnace.
2.1 Characterization techniques
The crystalline structure and phase of the thin film were
identified by X-ray diffraction using a PANalytical/Xpert3
powder XRD instrument. The surface morphology, shape,
and grain size were examined using a Zeiss (SIGMA), field
emission scanning electron microscope and elemental com-
position was determined using energy dispersive X-ray spec-
troscopy (EDS) attached to FESEM. The average roughness
(Ra), root mean square roughness (RMS), and grain size ana-
lyzed by atomic force microscope (AFM) in contact mode
using Agilent Technologies 5500. The optical properties of
the films were investigated by UV–Vis spectrometer using
ThermoFisher Evaluation 220 instrument. The room-tem-
perature photoluminescence (PL) measurements were per-
formed on Varian Cary Eclipse Photoluminescence analyzer.
Room-temperature Raman spectra were analyzed using a
Raman spectrophotometer. The current–voltage (I–V) meas-
urements were performed using a Keithley 2400 instrument.
3 Results and discussion
3.1 Structural analysis
Figure 1 reveals the XRD patterns of annealed MgO film
deposited at substrate temperature 300 °C, 350 °C, 400 °C,
and 450 °C. The XRD spectra reveal the polycrystalline
nature with the cubic phase of periclase MgO [40]. Further,
the broader diffraction peaks indicate the smaller crystallite
Journal of Materials Science: Materials in Electronics

JCPDS NO: 79-0612

The crystallite size is calculated from Scherrer’s formula
JCPDS NO: 76-1363
d * MgO D = k𝜆∕𝛽 cos 𝜃, (2)

(2 0 0)
# MgO2
* where ‘k’ is the Scherrer’s constant, ‘λ’ is the wavelength of
X-ray, ‘β’ is full width at half-maximum.

(2 2 2)
c
Intensity (a.u)

(2 2 0)
The dislocation density defined as the length of disloca-
#
* tion lines per unit volume of the crystal and calculated using
the equation:
b

𝛿 = 1∕D2 , (3)
a
where ‘D’ is the crystallite size.
The strain (ε) is calculated using the formula
( )
a − a0
35 40 45 50 55 60 65 70 75 80 Microstrain(𝜀) = × 100%, (4)
2 (degree)
a0

where a0 (4.212 Å) is the standard lattice constant of stoi-

Fig. 1  XRD patterns of MgO thin film deposited at a 300  °C, b chiometric MgO thin film, ‘a’ is the lattice constant of (2 0
350 °C, c 400 °C and d 450 °C
0) orientation.
The lattice constant can be found using the relation
size was observed. The peaks were observed at angle 2θ,
42.80º, and 62.13º. All the samples exhibit the textured ori- 1 h2 + k2 + l2
= , (5)
entation along (2 0 0) and (2 2 0) planes [2]. The MgO NR d2 a2
(nanorod) grown on SLS glass substrate in the particular
where (hkl) are the Miller indices of the given plane.
preferred (2 0 0) plane is reported [2]. The obtained peak
The volume of unit cell (V) is determined from the
position matches with the standard JCPDS card no: 79-0612.
relation
The film indicates the face-centered cubic structure with
space group Fm 3 m. V = a3 . (6)
Additionally, the presence of M ­ gO2 phase at 2θ = 66.18º
[JCPDS card: 76-1363] identified from the XRD patterns, The specific surface area (s) calculated by [49]
is found to increase with substrate temperature [41]. With 6 ∗ 103
increase substrate temperature, significant change in the s=
Dp 𝜌
,
peak intensity of (2 0 0), (2 2 0) and (2 2 2) reflection planes
is increased. The increase in the intensity of (2 0 0), (2 2 0) where ‘s’ is the specific surface area, ‘ρ’ is the density of the
and (2 2 2) planes denotes the improved crystallinity of the sample and ‘Dp’ is the particle size.
film which can be attributed to the influence of substrate The crystallite size (D), strain (ε), dislocation density (δ),
temperature [42]. The better crystallinity of sprayed MgO and the other parameters, the volume of the unit cell (V) and
film at low substrate temperature is reported by YidaYang lattice constant (a) are detailed in Table 1.
et al. [43]. The preferred orientational growth along (2 0 The crystallite size found from Scherrer’s formula for (2
0) plane might be due to internal stress and surface energy 0 0) plane are 11.10 nm, 5.44 nm, 12.44 nm, 18.99 nm for
[44]. Also, the textured orientation of the film along (2 0 the film deposited at substrate temperature 300 °C, 350 °C,
0) direction is attributed to the high packing density/factor 400 °C and 450 °C, respectively. The increase in the inten-
and minimum defects [45]. It is also noted that the textured sity of (2 0 0) reflection plane increases with substrate tem-
growth of film increased with an increase in substrate tem- perature signifying the crystallinity of thin film. Further, the
perature ascribing the internal structure orientation [46, 47]. increase in grain size resulting in the reduction of strain and
The surface area of (2 0 0) plane is much lower than the dislocation density is observed [50]. Higher crystallite size
other (2 2 0) plane [48]. leads to tensile strain, lower crystallite size exhibits com-
The d-spacing (d) can be evaluated from pressive strain [51]. The lattice parameter of MgO thin film
n𝜆 decreases with an increase in crystallite size, which is caused
d= , (1) by corresponding surface stresses [52]. The calculated and
2 sin 𝜃
experimental values of d-spacing are in close agreement
where ‘n’ is the order of reflection, and ‘θ’ is the angle of with each other.
reflection.

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 Journal of Materials Science: Materials in Electronics

Table 1  (hkl) plane, FWHM, 2θ, d-spacing, crystallite size (D), dislocation density (δ) and strain (ε) of MgO thin film
Substrate 2θ hkl FWHM Intensity d-spacing (Å) Crystallite Dislo- Strain Volume Lattice Surface area
temperature (deg) Å (cts) size (D) cation ε of parameter
(°C) (nm) density (%) unit cell (Å) (Å)
(1015
lines/m2)

300 42.85 200 0.632 718 2.108 14.10 5.03 0.142 75.063 4.218 121.58
62.15 220 1.021 382 1.492 9.48 11.12 179.29
350 42.56 200 1.635 1033 2.122 5.44 33.79 − 0.118 74.501 4.207 312.44
62.92 220 0.797 595 1.475 12.20 6.71 139.32
400 42.74 200 0.716 1485 2.113 12.44 6.46 − 0.023 74.673 4.211 134.72
62.58 220 1.596 958 1.482 6.08 27.05 279.55
450 42.35 200 0.468 1849 2.132 18.99 2.77 0.071 76.365 4.242 89.50
62.10 220 1.565 1239 1.493 6.18 26.18 275.03

3.2 Morphological characterization 3.4 AFM characterization

Figure 2a, c, e, g depicts the morphology of MgO thin film
deposited at different substrate temperatures 300 °C, 350 °C,
400 °C, and 450 °C by perfume atomizer. The surface mor-
phology of the deposited thin film is due to the atomic rear-
rangement of sprayed droplets during pyrolytic decomposi-
tion on the preheated glass substrate. The thin film samples
were annealed in air at 450 °C for 4 h, to improve the crys-
tallinity of thin film. And it promotes the formation of clus-
ters or islands on the film and tensile or compressive strain
[53]. A series of changes in the morphology of MgO thin
film with substrate temperatures are observed. Figure 2a, c
shows that the film consists of some irregular grains with
large clusters embedded on the surface. However, the close
inspection of the morphology of MgO thin film at lower sub-
strate temperature shows intergranular voids or pores on the
surface of the film. At high substrate temperature (Fig. 2e,
g), the voids disappear and the base of the film contains
tightly packed, small spherical grains evenly distributed on
the entire film’s surface over which the isolated irregular
grains are grown [44, 54, 55]. The bigger grains are due to
Oswald ripening process [78].
3.3 Elemental distribution
The EDS spectra shown in Fig. 2b, d, f, h give elemental dis-
tribution up to a few layers from the surface of the thin film.
The distribution is taken randomly at a particular location.
The spectrum shows the inhomogeneous distribution of Mg
and O on the MgO surface. The atomic and weight % of O
and Mg presented in Table 2 describe the nonstoichiometric
MgO. The atomic % of Mg and O suggests a deficiency of
Mg cation vacancies in MgO films [56]. This data are in line
with that obtained by Valanarasu et al., for MgO thin films
deposited by spin-coating [27]. All the films have a high O/
Mg ratio describing the nonstoichiometric MgO films [70].
AFM characterization is an outstanding analytical technique
for the study of different surface morphology and texture of
the thin film. A series of changes in the AFM topographi-
cal images of MgO thin film deposited at different substrate
temperatures are displayed in Fig. 3a–h. The clusters of
spherical shaped grains with narrow size distribution are
seen from the images. The bright spot on the surface of the
film represents the MgO crystallites grown relatively on the
grain morphology [57]. The homogeneous, smooth surface
of the thin film displayed in Fig. 3a, b represents evenly
distributed grains across the film’s atomically flat surface.
The spherical shaped grains in the cluster formed in a par-
ticular area are shown in (Fig. 3c, d). The spherical shaped
grains are segmented like a thread topology observed in
Fig. 3e, and from the 3D image (Fig. 3f) the faceted colum-
nar microstructure were identified, maybe attributed to the
increased roughness of the MgO film at 400 °C. This may
be ascribed to anisotropy and mobility of ad-atoms [20].
The distinct spherical grains with well-defined boundaries
are observed from Fig. 3g. The surface roughness of the
MgO thin film increases with the substrate temperature.
Hence, the film is suitable for gas sensors and photocata-
lytic applications.
The parameters such as root mean square roughness (Rq),
average roughness (Ra), maximum peak to valley height (Rt),
mean height roughness (Rz), roughness skewness (Rsk) and
roughness kurtosis (Rku) are listed in Table 3.
The negative skewness value of MgO film indicates the
film with a well-defined surface. Thus from the Ra values
and Fig. 3b, f, the film deposited at substrate temperature
400 °C and 300 °C reveals the rougher and smoother surface
of MgO thin film and the Rku is negative indicating the film
surfaces are bumpy [58].

13
Journal of Materials Science: Materials in Electronics

5500
(b)
5000
a
4500

4000

3500 O

Intensity (cps)
3000

2500 Mg
Si
2000

1500

1000

500

0
1 2 3 4 5
Energy (KeV)

5500
(d) Si
5000

4500
c
4000
Intensity (cps)

3500

3000 O

2500 Mg

2000

1500

1000

500

0
1 2 3 4 5
Energy (KeV)

Fig. 2  a, c, e, g SEM images and their corresponding EDS spectra (b, d, f, h) spectra of MgO thin film at substrate temperatures a 300 °C, b
350 °C, c 400 °C, and d 450 °C

3.5 Optical characterization strong absorption in the UV region at around 309 nm for

Figure 4 explores the UV–Vis absorbance spectra of MgO
thin film deposited at different substrate temperatures
300 °C, 350 °C, 400 °C, and 450 °C and annealed at 450 °C
for 4 h. The spectra were recorded in the wavelength range
of 200–800 nm. Mostly, the absorption spectra may be split
into three regions: (i) strong absorption, where λ ≤ 390 nm.
Here an electron absorbs energy from incident photons and
move over to the conduction band, leaving behind a hole in
the valence band, thus forming an exciton; (ii) absorption
tail region from 390 nm ≤ λ ≤ 570 nm, the electrons cross
over to shallow states below the conduction band and (iii)
weak absorbing region, λ > 570 nm [59]. The absorption
occurs when the electrons absorb incident energy and is
excited to the higher energy state. The MgO film exhibits
all the films enumerating the semi-crystalline nature of the
film. And peaks are observed at wavelengths around 298 nm,
346 nm, and 344 nm, respectively, for the films at different
substrate temperatures. This may be accorded to absorp-
tion by structural defects and bandgap absorption [60–63].
A similar spectral trend of irradiated MgO thin films was
reported [64]. The former is assigned to the primary band-
gap which is attributed to the transition from 1s light hole
level to lowest 1s electron level. The secondary absorption
peak is related to the secondary bandgap. This may due to
the transition 1s heavy hole to lowest electron sub-band
level [65]. Almost zero absorbance in the wavelength range
350–800 nm is observed for all spectra [66, 67]. As the
particle size decreases, the absorption wavelength shifted
to the shorter wavelength region is evidenced from Fig. 4,

13
 Journal of Materials Science: Materials in Electronics

5500
Si
e 5000
(f)

4500

4000

Intensity (cps)
3500

3000
Mg
2500

2000

1500
O
1000

500

0
1 2 3 4 5
Energy (KeV)

5500
(h)
5000
g
4500

4000
Si
Intensity (cps) 3500
O
3000

2500 Mg
2000

1500

1000

500

0
1 2 3 4 5
Energy (KeV)

Fig. 2  (continued)

Table 2  Atomic and weight % Ts Atomic % Weight %

of MgO thin film
O Mg Si O Mg Si

300 54.93 33.35 11.72 45.33 37.7 16.97

350 54.19 31 14.81 45.38 32.67 21.95
400 54.15 31.64 14.21 45.75 33.18 21.07
450 58.06 21.91 20.03 46.92 28.42 24.66

confirming the quantum confinement effect [68]. Thus the
optical excitation of the surface of MgO film [69]. Moreover,
Rastogi et al. [70] reported that the absorbance band in the
range of 200–450 nm is due to their defect states.
Figure  5 displays the UV transmittance spectrum of
MgO film deposited at various substrate temperatures. It
is observed that the overall transmittance of above 70% is
seen for the deposited MgO film [71]. The highest transmit-
tance is observed for the film deposited at lower substrate
temperature, i.e., 300 °C and the least transmittance noticed
for the film at substrate temperature 400 °C is due to higher
defect concentration [45], thereby resulting in the reduction
of optical bandgap values [27].
Ramana et al. [72] have also pointed out that film with
crystallite size (≤ 50 nm) shows a high degree of optical
transmittance. Since the transmittance of magnesium tin
oxide is above 70%, it can be used as a protective coating
instead of an expensive ITO [73].
The variation in bandgap energy Eg of MgO film depos-
ited at different substrate temperatures is displayed in Fig. 6.

13
Journal of Materials Science: Materials in Electronics

Fig. 3  a–h 2D and 3D topographical images of MgO thin film deposited at different substrate temperatures

13
 Journal of Materials Science: Materials in Electronics

Fig. 3  (continued)

Table 3  AFM parameters Substrate tempera- Rq Ra Rq/Ra Rsk Rt Rz Rku

ture (°C) nm nm nm nm
(TS)

300 270.9 240.9 1.125 − 0.66 246.3 748 − 0.557

350 300.9 284.1 1.059 − 0.33 288.2 1180 − 1.380
400 327.0 305.9 1.068 − 0.376 306.9 386 − 1.437
450 321.3 297.6 1.079 − 0.401 302.9 631 − 1.343

Energy (eV) 100

4.0 3.8 3.6 3.4 3.2
1.8

1.6
M300 80
M350
M400
Transmiance (%)

1.4
M450
1.2 60
Absorbance (a.u)

M300
M350
1.0
M400

0.8
40 M450

0.6 344 nm
20
0.4
346 nm

0.2
350 400 450 500 550 600 650 700 750 800
0.0 Wavelength (nm)
320 340 360 380 400
Wavelength (nm)
Fig. 5  Transmittance spectra of MgO thin film deposited at a 300 °C,
b 350 °C, c 400 °C and d 450 °C
Fig. 4  UV–Vis absorbance spectra of MgO thin film deposited at a
300 °C, b 350 °C, c 400 °C and d 450 °C

13
Journal of Materials Science: Materials in Electronics

25 0.03
M300
M300
M350
20 M350
M400
M400
M450
M450
15 0.02
2
( h ) (eV/cm)

Reflectance
10
2

5 0.01

3.7 3.8 3.9 4.0 4.1 4.2 4.3 4.4

300 350 400 450 500
Energy (eV)
Wavelength (nm)

Fig. 6  Bandgap variation of MgO thin film at a 300 °C, b 350 °C, c

Fig. 7  Reflectance spectra versus Wavelength (λ) of MgO thin film
400 °C and d 450 °C

The bandgap Eg values are obtained from well-known

√
)2
1+R 4R
(
Tauc’s plot method using the relation: n= + − k2 , (8)
1−R 1−R
)n
(7)
(
𝛼h𝜈 = A h𝜈 − Eg , where ‘n’ is the reflectance and ‘k’ is the extinction coef-
ficient or absorption index.
where ‘α’ is the absorption coefficient, ‘hν’ is the energy
The index of absorption (k) is calculated using the relation
of the photon, Eg is the bandgap of the material, A is the
energy-dependent constant and n takes the integer value 𝛼𝜆
k= . (9)
depending on the nature of electronic transition (n = ½, 2.. 4𝜋
for direct and indirect allowed transitions). For MgO thin
The index of absorption (k) of MgO thin film exhibits a
film, the ‘n’ corresponds to direct electronic transition [57].
peak around 310 nm and then decreases. MgO thin films
Figure 6 shows the energy gap variation of energy (hν)
have shown a unique behavior in the refractive index and
vs (αhν)2. MgO thin films possess two segments. The first
it shows values ranging from 0.96 to 1.06, which are low
(Eg2) around 3.5–3.8 eV is due to sub-band gaps from the
compared to bulk MgO [77–79].
secondary phase [74], whereas the second Eg1, from 4.0 to
The low value of the refractive index may be related to
4.4 eV, is the difference in energy levels between conduc-
inhomogeneous stoichiometry of O/Mg [80]. Initially, the k
tion band minimum and valence band maximum [75]. The
value was found to decrease with wavelength around 400 nm
obtained bandgap value is lower compared with the bulk
in the UV–visible region and becomes saturated in the
MgO (7 eV), and it could be due to the presence of anion and
infrared region of wavelength 450–800 nm. The value of k
oxygen vacancies and is related to the density of localized
(Fig. 8) lies in the range 0.07–0.69 indicating high transpar-
states [76]. The MgO thin film presents the large bandgap
ency of thin film as seen from the transmittance spectra [81].
energy value of 5 eV and a low energy bandgap value rang-
A similar trend is observed for the refractive index (n). This
ing from 3.81 to 3.92 was reported [27, 33].
may be of technological importance as it is adapted for opto-
The reflectance spectra of MgO thin film as the function
electronic devices, switches, filters, photonic devices, etc.
of wavelength (λ) are depicted in Fig. 7. As seen from the
spectra, the reflectance decreases with the substrate tempera-
3.6 Photoluminescence analysis
ture which is attributed to interband transition.
The refractive index is used to examine the electrical and
The phenomenon of electron–hole recombination can be
optical properties of the material. It is related to the elec-
best explained by photoluminescence spectroscopy. Photo-
tronic polarization of ions and the local field of the material.
luminescence spectra measure the intensity of emitted radia-
The refractive index (n) for MgO thin film was evaluated
tion as a function of either the excitation wavelength or the
using the formula

13
 Journal of Materials Science: Materials in Electronics

120
(a)

360
4
M300 M300
100
M350
M350
index of absorption (k)

M400
3 M400

376
M450 80 M450

PL Intensity (a.u)
2 60

535
519
40

505
1

494
459
20

0
0
400 500 600 700 800 350 400 450 500 550 600
Wavelength (nm) Wavelength (nm)

Fig. 9  Room-temperature PL spectra of MgO film deposited at sub-

1.4 (b)
strate temperatures 300 °C, 350 °C, 400 °C, and 450 °C

1.2

at higher substrate temperature, whereas the intensity of

Refractive index (n)

1.0

0.8
0.6
0.4
0.2
0.0
400 500 600
Wavelength (nm)
Fig. 8  Variation of a index of absorption and b refractive index of
MgO thin film
emission wavelength. Figure 9 represents the photolumines-
cence spectra (PL) of typical periclase MgO thin film depos-
ited by perfume atomizer at various substrate temperature.
Several intense peaks were observed around 360–600 nm
wavelength range. Almost all the spectra of the MgO thin
film have a similar spectral shape with no difference except
the intensity. The strong and broad UV peaks were observed
at 360 nm for all the samples is due to exciton process. The
other PL bands in the visible–IR region could be due to vari-
ous structural defects and not due to the bandgap emission.
The emission peaks are identified at 459, 494, 505, 519,
535 nm, which fall under the blue and green region of the
electromagnetic spectrum.
As the substrate temperature increases, the intensity of
the emission peaks decreases. The band at the blue region
(459 nm) associated with structural defects [82] vanishes
M300 other peaks 494, 505, 519, and 535 nm, decreases. The blue
M350 emission band centered at around 459, 494 nm arises from
M400 the recombination of photogenerated holes with electron
M450 occupying the oxygen vacancy and is attributed to F2+ 2 cent-
ers. The green emission band at around 505 and 519 nm is
due to oxygen ion vacancy (F centers) [1]. The PL band
at around 534 nm is due to oxygen vacancy due to transi-
tion from [83] 1T1u → 1A1g (F center). The variation in the
peak intensity is related to the presence of oxygen and Mg
700 800 vacancy defects in the sample, whereas at different tempera-
tures, the change in the intensity and the properties optical
quality, energy transport is observed [84, 85]. The PL bands
are blue-shifted when compared with the bulk MgO, clearly
stating the reduced average crystallite size as evidenced from
XRD results. The PL emission spectrum of MgO thin films
lies in the visible region which could be used in optic display
device and LED applications [34].
3.7 Raman analysis
Raman spectroscopy is a versatile nondestructive technique
to investigate the vibrational and structural properties of thin
film. Room-temperature Raman spectra of prepared MgO
films are shown in Fig. 10. MgO has O ­ h point group sym-
metry and the polarization tensor has irreducible representa-
tions A1g, Eg, and T2g [86].
The existence of the cubic phase in MgO film was ana-
lyzed by the Raman spectrum. From group theory, the
Raman active modes are
T1u xT1u = A1g + Eg + T1g + T2g .

13
Journal of Materials Science: Materials in Electronics

50000 M450 at various substrate temperatures, such as 300 °C, 350 °C,

400 °C, and 450 °C.

1096

2438
M400 The current (I) increases linearly with the applied voltage

2885
40000 (V) shows the semiconducting behavior of the MgO thin
Raman Intensity (a.u)

472
M350
film [90]. The larger forward current for the given voltage
implies the higher conductivity of the film which leads to
30000 higher efficiency in the solar cells [91]. The presence of
M300
defect type is responsible for I–V characteristics [92]. The
I–V characteristics resulting in nonlinear, asymmetric, and
20000 hysteretic behavior for PCMO (­ Pr1-xCaxMnO3) device which
are used in resistive switching were reported [93]. The elec-
trical resistivity of the film is found to decrease with sub-
10000 strate temperature. This may be attributed to the crystalline
500 1000 1500 2000 2500 3000 3500 4000 nature of the film [94].
-1
Raman Shift (cm )

Fig. 10  Room-temperature Raman spectra of MgO thin film 4 Conclusion

The MgO thin film is deposited on a glass substrate using

M300
perfume atomizer. The influence of the substrate temperature
1.20E-010
M350 on the spray-deposited MgO thin film was studied. XRD
1.00E-010
M400
M450
results show the cubic structure of periclase MgO with pre-
ferred orientation along (200) plane. The presence of ­MgO2
8.00E-011 phase is also identified and the intensity of (2 2 2) reflec-
Current (amps)

tion plane of ­MgO2 is found to increase with the substrate

6.00E-011
4.00E-011
2.00E-011
0.00E+000
0 5 10
Voltage (Volt)
Fig. 11  I–V characteristics of MgO film at different substrate tem-
peratures
The prominent Raman peaks were identified at 472, 1096,
2438 cm−1, and shoulders at 2885 cm−1. The band centered
around 472 cm−1 is assigned to E2 (high) first-order Raman
modes. The weak D and G bands are observed for MgO
films. The intensity of Raman peaks increases with substrate
temperature. The breathing mode known as D band is identi-
fied below 1500 cm−1. The symmetrical stretching vibration
band (ν1) centered at 1096 cm−1 is attributed to TO–LO
surface phonon modes in MgO lattice [87, 88]. The band
around 2880 cm−1 corresponds to C–H stretching mode [89].
3.8 Electrical properties
Figure 11 shows the variation in typical current (I)–volt-
age (V) response of MgO film under forward bias deposited
temperature. The crystallite size for (2 0 0) plane is found to
be 14.10 nm, 5.44 nm, 12.44 nm, and 18.99 nm. The depos-
ited MgO thin films having both compressive and tensile
strains were identified. The surface with spherical grains is
found from FESEM and is well correlated with AFM. The
15 20
strong absorbance at 309 nm and peaks in the absorption
tail region displayed in absorbance spectra were due to the
defect state and interband absorption. The MgO thin film
shows reasonable transmittance of about 70%. The MgO
thin film possesses two segments of bandgap, first Eg in the
range 3.5–3.8 eV and the second Eg ranging between 4.0 and
4.4 eV. The calculated band gap values are close to metal-
lic conduction behavior. The presence of a green emission
band is identified in PL studies. The linear response over
I–V measurements shows the semiconducting behavior of
the MgO thin film.
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