Materials Research Express

PAPER

Synthesis and characterization of magnesium aluminate (MgAl2O4)

spinel (MAS) thin films
To cite this article: Syed Muhammad Ahmad et al 2018 Mater. Res. Express 5 016415

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 Mater. Res. Express 5 (2018) 016415 https://doi.org/10.1088/2053-1591/aaa828

PAPER

Synthesis and characterization of magnesium aluminate (MgAl2O4)

spinel (MAS) thin films
RECEIVED
24 December 2017
REVISED
9 January 2018
ACCEPTED FOR PUBLICATION
Syed Muhammad Ahmad1,2,3 , Tousif Hussain1, Riaz Ahmad1 , Jamil Siddiqui1 and Dilawar Ali1
16 January 2018 1
Centre for Advanced studies in Physics (CASP), GC University, Lahore, Pakistan
2
PUBLISHED Department of Physics, GC University, Lahore, Pakistan
3
29 January 2018 Department of Physics, The University of Lahore, 1-Km Raiwind Road, 54000 Lahore, Pakistan
E-mail: ahmad4u19@ymail.com and muhammad.ahmad4@phys.uol.edu.pk

Keywords: MAS thin film, DPF, XRD, FTIR, SEM, Vickers micro hardness tester

Abstract
In a quest to identify more economic routes for synthesis of magnesium aluminate (MgAl2O4) spinel
(MAS) thin films, dense plasma focus device was used with multiple plasma focus shots. Structural,
bonding between composite films, surface morphological, compositional and hardness properties of
MAS thin films were investigated by using x-ray diffraction (XRD), Fourier transform infrared
spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive x-rays (EDX) analysis
and Vickers micro hardness test respectively. In XRD graph, the presence of MgAl2O4 diffraction
peaks in crystallographic orientations (222), (400) and (622) pointed out the successful formation of
polycrystalline thin films of MgAl2O4 with face centered cubic structure. The FTIR spectrums showed
a major common transmittance band at 697.95 cm−1 which belongs to MgAl2O4. SEM micrographs
illustrated a mesh type, granular and multi layers microstructures with significant melting effects.
EDX spectrum confirmed the existence of magnesium, oxygen and aluminum in MAS films. A
common increasing behavior in micro-hardness of composite MgAl2O4 films by increasing number
of plasma focus shots was found.

1. Introduction

In recent few years, magnesium aluminate (MgAl2O4) spinel (MAS) has accepted a great interest from
researchers and the industrial sector on behalf of its excellent mixture of numerous properties: such as higher
melting point (2135 °C), comparatively low density (3.58 g cm−3), huge hardness (16 GPa), great mechanical
strength (135–216 MPa) at room temperature as well as at raised temperature (120–205 MPa) at 1300 °C, high
resistance versus chemical assault, quite low thermal expansion coefficient (9 ×10−6 °C) amid 30 °C and
1400 °C, broad energy band gap, great thermal-shock resistance, excellent chemical stability, higher electrical
resistivity [1–6]. MAS with cubic crystal structure accompanied with numerous above stated unique properties
made it an essential material like in domes, optically transparent windows, armours, humidity sensors,
refractory of high-pressure discharge lamps and ceramics. MAS thin films also utilize as buffer layers and tunnel
barriers in ferroelectric and superconducting films [7–9]. There are several reports available in the consumption
of MAS as catalysts in the fields of environmental catalysis, fine chemicals production and petroleum
processing [10, 11].
MAS thin films have been already synthesized by several physical and chemical techniques such as: sol-gel,
conventional solid-state-reaction, metal-organic chemical vapor deposition, polymeric precursor synthesis,
aerosol method, spray pyrolysis, spark plasma sintering, pulsed laser deposition and organic gel-assisted citrate
complexation except dense plasma focus (DPF) [12–20]. DPF is an uncomplicated, economical plasma device
which is recognized as a pulsed-plasma appliance. It is an origin of production for relativistic electrons, x-rays,
energetic ion beams and neutrons which are utilized for material processing [21]. The DPF has been utilized for
numerous applications in several fields such as: thin-film deposition [22], surface modification [23], ion

© 2018 IOP Publishing Ltd

Mater. Res. Express 5 (2018) 016415 S M Ahmad et al

Figure 1. Schematic diagram of dense plasma focus (DPF) device used for the thin film deposition of MAS.

implantation [24], and thermal surface treatment [25]. In the current reported study, first time DPF deposition
method has been used for synthesized the MgAl2O4 thin films.

2. Experimental setup

A Mather sort of DPF device (figure 1) is utilized in the current reported experiment which is powered by means
of a Maxwell capacitor (15 kV, 30 μF). The operational parameters of the used DPF were in this mode: the
operational voltage was set at 12 kV which produced the input energy value of about 2.3 kJ with maximum
discharge current about 175 kA. Inductance of the used equipment was about 80 nH. DPF chamber was
evacuated up to ∼1×10−2 mbar through a rotary vane pump. Afterward, chamber was filled up with highly
pure oxygen gas at optimal pressure of 0.75 mbar. A solid copper made cylindrical anode is used inside DPF
chamber which is encircled by six cylindrical copper made cathode rods. For the deposition of MgAl2O4 thin
films, the centrally hollow copper anode was capsulated by magnesium target at its top. The working canon of
DPF machine is elucidated as follows.
The major function of DPF device is rooted upon the electric-pulse discharge of capacitor throughout the
gas among two coaxial electrodes. For polarization, a pyrex build sleeve is utilized which facilitates in the
formation of uniform current sheath. After apply high voltage (HV) across electrodes, the electrical gas
breakdown arises around sleeve, ultimately a current-sheath appears. This current-sheath goes up towards
opening ends of assembled electrodes by J×B force. When this current-sheath arrives at the top of electrodes
then it radially collapses and as a result, a short lived hot dense plasma forms at the front of anode tip.
A very severe electric field coupled with magnetic field induces owing to quick changes arising in the
inductance of short-lived pinched plasma whose creation pursues through the beginning of sausage instabilities.
The generated electric field causes to accelerate ions and electrons in opposite direction in such a way that ions
upward to the chamber while electrons towards the anode [26]. From plasma column, these emitted relativistic
electrons cause to ablate the magnesium from the tip of anode. Then ablated magnesium may interact with
oxygen ions of same shots, which later interact with aluminum to form MgAl2O4.
Aluminum samples were used as substrate having 10×10×5 mm3 dimensions. All samples were washed
by ultrasonic bath of acetone for 10 min prior to placing inside chamber. Afterward, samples were raised at the

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Mater. Res. Express 5 (2018) 016415 S M Ahmad et al

Figure 2. XRD patterns of MgAl2O4 films exposed to different number of focus shots.

distance of 5 cm from the anode tip with the help of a sample holder inside chamber. The deposition for
MgAl2O4 thin films is attained using 5, 10, 15, 20, 30 and 40 plasma focus shots. To evade redundant exposure of
samples during taken plasma focus shots to achieve fine focusing, an adjustable shutter is sited amid anode and
substrate, displaced subsequently gaining fine focusing. To monitor and trace the voltage and current
waveforms, Rogowski coil along with HV probes were utilized. Tektronix TDS 3054B oscilloscope (5 GS s−1,
500 MHz) was employed to preserve signals coming from Rogowski coils and HV-probe during experiment.
The record current and voltage signals were utilized for accumulation motives of DPF device.
Structural, surface morphological, compositional, bonding between composite films and hardness
properties of MgAl2O4 thin films were investigated by using x-ray diffraction (XRD), scanning electron
microscopy (SEM), energy dispersive x-rays (EDX) analysis, Fourier transform infrared spectroscopy (FTIR)
and Vickers Micro Hardness analysis (ASTM E 384) respectively.

3. Results and discussions

3.1. XRD analysis

The crystalline orientations spectra of deposited MgAl2O4 from DPF with multiple plasma focus shots (5, 10, 15,
20, 30 and 40) have been achieved by Phillips X’Pert PRO MPD XRD. XRD was operated at: voltage (40 kV),
current (40 mA) using CuKα of 1.540598 Å and scanning mode was fixed over the range of 2ϴ=20°–80°
(figure 2).
In XRD graph, the presence of MgAl2O4 diffraction peaks in different crystalline orientations of all deposited
samples point out the successful formation of polycrystalline thin films of magnesium aluminate (MgAl2O4)
with face centered cubic structure. We gained peaks at angles: 31.4°, 38.6°, 44.8°, 65.2° and 78.2° corresponding
to crystallographic orientations (220), (222), (400), (440) and (622) respectively. The above XRD results exhibit
the successful grow of polycrystalline MgAl2O4 thin films as they are processed with exceeding plasma focus
shots.
During the deposition of polycrystalline thin films of MgAl2O4 by DPF, three processes may occur: (1)
oxygen ions accelerate towards aluminum substrates transport energy immediately, causing high thermal
gradient. As a result, heating and cooling rates are building up inside surfaces’ layer of aluminum. The particular
oxygen ions are foundation of etching and cleaning of substrate surface former to deposition. After that
promising oxygen ions-implantation occur which are the responsible of formation of Al2O3 phase. (2) Electrons
accelerate towards magnesium anode, ablated magnesium from anode. Then ablated magnesium from anode
tip can interact with oxygen ions of same shots form MgO which later interact with aluminum to form MgAl2O4.
(3) Formation of MgO owing to oxidation of magnesium atoms by vigorous oxygen ions from same shots and
deposited on aluminum (Al) substrate [27]. XRD results confirm that 2nd process is dominant in our case.
Figure 2 exhibits that when the number of plasma focus shots increasing from 5 to 40, the diffraction peaks at
(222), (400) and (622) increasing in intensity. However, we can say that the peak sharpness and intensities are
increased with increasing of several numbers of plasma focus shots. So the observed diffraction pattern revealed
the crystallinity of the films, which are increased with increase of several number of focus shots. This raise in

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Mater. Res. Express 5 (2018) 016415 S M Ahmad et al

Table 1. Crystallite size calculated for MgAl2O4 as a function of

number of plasma focus shots.

Magnesium aluminate
(MgAl2O4) crystallite size
calculated from different
XRD planes(nm)

No. of shots (222) (400) (622) Mean size (nm)

5 shots 19.5 24.7 21.5 21.9±1.09

10 shots 25.1 24.8 21.1 23.6±1.18
15 shots 25.2 24.6 21.8 23.8±1.19
20 shots 23.7 22.7 20.7 22.3±1.11
30 shots 23.8 21.9 20.0 21.9±1.09
40 shots 25.5 23.5 20.5 23.1±1.16

intensity of the diffraction peaks at (222), (400) and (622) is due to greater ion flux which is moved to substrate.
As a result enhance crystallization of MgAl2O4 phases occurred. Wiedwald et al [28] has accounted that the
improve crystallization of a synthesized material is related with diminution in the activation energy (ED). This
reduction in the activation energy (ED) possibly attained by increasing the number of point defects, for example:
vacancy and interstitial inside crystal structure. Through successive plasma focus shots, vigorous ion-irradiation
of the deposited material produces a higher concentration of defects in the deposited film material.
Consequently for diffusion, ED is supposed to diminish for synthesized films with optimum number of focus
shots. We also observe a decrease pattern in the intensity along (220) and (440). XRD peaks at (220) and (440)
correspond to aluminum (Al) substrate. With increasing number of focus shots, peaks intensity of MgAl2O4 thin
films increases, while intensity of substrate peaks decreases respectively. Similar trend of decreasing substrate
peaks with increasing number of plasma focus shots have been reported by Ramezani et al [29] in which they
have observed the effect of plasma focus shot on coating of magnesium nitride on stainless steel substrate. As
number of plasma focus shots increases, the growth of MgAl2O4 coating on aluminum substrate increases,
which ultimately covers the substrate surface and is responsible for decrease in the peak intensity of substrate
with increasing focus shots [29, 30].
The crystallite size of deposited polycrystalline thin films of magnesium aluminate (MgAl2O4) is measured
by using the Scherrer’s formula [31]

Kl
Crystallite size = ,
b Cos q

where K=0.93 is the numerical constant, l =1.54 Å is the wavelength of x-ray source, b is the FWHM (rad)
of the diffraction peak and q is the Bragg’s angle.
Table 1 represents the estimated crystallite size of deposited magnesium aluminate (MgAl2O4) with 5% error
for (222), (400) and (622) diffraction reflections with various focus shots.
From table 1 we can see that when plasma focus shots were increased from 5 to 15 shots, MgAl2O4 mean size
was also increased from 21.9 to the maximum value of 23.8 nm due to thermal annealing effect of focus shots.
Subsequently, when plasma focus shots reached to 40 shots, MgAl2O4 mean size decreased to 23.1 nm. Table 1
clearly shows that mean crystallite size does not show significant variation with change in focus shots. The
smaller average mean crystallite size can be attributed to the transient annealing by pulsed ion irradiation [32].

3.2. FTIR analysis

Figure 3 illustrates the Fourier transform infrared spectra of different magnesium aluminate (MgAl2O4) films
deposited for 5, 15 and 30 plasma focus shots and of substrate with them for comparison. FTIR spectrum of
MgAl2O4 films for multiple plasma focus shots is recorded between 650 and 4000 cm−1. The FTIR spectrums of
all deposited films showed a major common transmittance bands at 697.95 cm−1 which do not exist in
substrate’s spectrum. This noted transmittance band at 697.95 cm−1 correspond to the existence of AlO6 groups
which build up the MAS, lie in crystallite phase. The width of absorption peaks has range from 671 to 715 cm−1
in the present work. Previous related literatures support these result [33, 34] and proves the successful
fabrication of MgAl2O4 films.

3.3. SEM analysis

SEM JEOL JSM-6480 LV with EDX attachment has been employed to examine the surface morphology of
magnesium aluminate (MgAl2O4) thin films.

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Mater. Res. Express 5 (2018) 016415 S M Ahmad et al

Figure 3. FTIR pattern shows an intense band at 697.95 cm−1 of MgAl2O4 films deposited for 5, 15 and 30 focus shots and untreated
substrate.

Figure 4 illustrates the SEM micrograph of MgAl2O4 films deposited for several (5, 10, 15, 20, 30 and 40)
plasma focus shots. For 5 focus shots, the surface morphology of deposited film (figure (a)) illustrates a mesh
(net) kind of micro-structure. This mesh type micro-structure contains two regions: (i) bright and (ii) dark. The
majority area of such micro-structure is occupied by bright regions whereas remaining area is occupied by
different dimensions of dark craters. Yet, a uniform and smooth film surface is detected.
For 10 focus shots (figure (b)), a granular surface structure of deposited film is observed. Deposited film
appears to be dense and showing some dark craters.
Surface morphology for the MgAl2O4 film synthesized with 15 plasma focus shots (figure (c)) exhibits the
existence of agglomerates of grains and distributed randomly above the whole film surface. A deep examination
of agglomerated particles tells that they contain grains and grew normal to the sample surface with variant rates,
therefore ensuing in rough surface. With increasing number of focus shots (10 to 15), the growth in mean size of
the grain agglomerates is owing to extensive total energy delivered to the film surface and larger transient
annealing as increased number of plasma focus shots.
For 20 focus shots (figure (d)), the surface morphology of composite thin film modifies notably as it emerges
much uneven and contains large size agglomerates of grains caused by enhanced irradiation dose. Thus, the
deposited film remains dense but non uniform in nature might be owing to increase of particulates with variant
rates.
The surface micrograph of MgAl2O4 film deposited for 30 and 40 plasma focus shots (figures (e) and (f))
shows the formation of grains and multi layers with significant melting effects. Films seem to be dense but not so
smooth in nature; because bigger particulates still exist accompanied by big clusters growing normal to the film
surface. Clusters appearance confirms that MgAl2O4 films consist of multi layers.
It is clear that surface structure morphologies and grains size of MgAl2O4 films varied with multiple plasma
focus shots. Each Focus shot causes to heating up the transient substrate surface with energetic ions to many
thousand degrees centigrade within a extremely short time, without delay pursued by quick melting and re-
solidification [35]. Accordingly, ion-irradiation is the process of transient thermal annealing that causes the re-
arrangement of atoms in deposit surface layer. This transient thermal annealing through energetic ions
attributes to atomic diffusion upon deposit surface layer attributing to creation of grains as observed in (figure
(b)) for 10 plasma focus shots irradiation. By increasing the number of plasma focus shots higher transient
annealing of the deposit surface layer is attained responding in grains agglomerates transform to larger
agglomerates as noticed clearly in (figures (c) and (d)) for 15 and 20 focus shots irradiation. The growth in the
mean size of grains agglomerates by increasing the number of plasma focus shots may be attributed to more
target material being ablated with increasing the number of plasma focus shots [36]. The films surface for 30 and
40 focus shots are notably melted owing to higher energetic ions in every focus shot and produced multi layers.
This may be attributed to re-sputtering of synthesized films and re-crystallization of aluminum phases [37].
Similar kind of surface morphology has also been accounted by Khan et al [38].

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Mater. Res. Express 5 (2018) 016415 S M Ahmad et al

Figure 4. SEM micrographs showing grains of different dimensions of MgAl2O4 films deposited for multiple (5, 10, 15, 20, 30 and 40)
focus shots and untreated aluminum substrate.

3.4. EDX analysis

In order to investigate the compositional analysis, EDX has been employed. The EDX spectrum confirms the
existence of magnesium, oxygen and aluminum in composite film. The quantitative deviation in the elemental

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Mater. Res. Express 5 (2018) 016415 S M Ahmad et al

Table 2. Elemental percentage of magnesium, oxygen and aluminum present in films.

Number of plasma focus shot

Elemental % 5 shots 10 shots 15 shots 20 shots 30 shots 40 shots

Mg (at%) 2.88 3.32 5.89 9.79 12.53 17.47

O (at%) 0.96 9.85 15.64 16.22 25.94 32.72
Al (at%) 96.16 86.83 78.46 73.99 61.53 49.81

Figure 5. EDX spectrum of the MAS film deposited by forty plasma focus shots.

percentage of magnesium, oxygen and aluminum elements present in the synthesized films with different
plasma focus shots is exhibited in table 2.
It is found that magnesium and oxygen contents grow with increasing the number of deposited focus shots
utilized for synthesized film. However greatest concentration of both elements is determined in the synthesized
film with forty (maximum) plasma focus shots which can be interpreted as the maximum coating of magnesium
with oxygen on the aluminum substrate.
A typical EDX spectrum of MgAl2O4 thin film deposited by forty plasma focus shots is illustrated in the
figure 5.

3.5. Vickers hardness analysis

Figure 6 illustrated the Vickers micro-hardness (MPa) report of MgAl2O4 composite films for (5, 10, 15, 20, 30
and 40) deposited focus shots at load 25 g. A common increasing behavior in micro-hardness of composite
MgAl2O4 films by increasing number of plasma focus shots is viewed. For forty plasma focus shots, the micro-
hardness of MgAl2O4 film is found to be 1087 MPa which is almost two times the micro-hardness of untreated
aluminum. The enhanced micro-hardness of synthesized films could be interpreted to the crystallinity growth of
MgAl2O4. We have already discussed such rising behavior in crystallinity of MgAl2O4 phases with increase in
number of plasma focus shots owing to intense ion flux transmitted to synthesized films and shown in XRD
spectra (figure 2). The major reason for the progress in micro-hardness of MgAl2O4 composite films can be
attributed to the increase in oxygen and magnesium contents with increasing plasma focus shots as former
reported in the EDX analysis. Moreover, the progressed micro-hardness of MgAl2O4 composite films might be
attributed to lattice distortions, vacancies and point defects. In fact, aluminum lattice is distorted by means of
interstitially integration of oxygen ions with ion induced collision cascades, building point defects in each

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Mater. Res. Express 5 (2018) 016415 S M Ahmad et al

Figure 6. Micro-hardness (MPa) of MgAl2O4 composite films deposited for (5, 10, 15, 20, 30 and 40) focus shots.

plasma focus shot. Yet, the doping of sputtered Mg into Al matrix also increases these point defects. Lattice
distortions and point defects prevent the motions of dislocation which causing the improvement in micro-
hardness of MgAl2O4 composite films. However, the raising micro-hardness values in present report shows the
formation of compact polycrystalline MgAl2O4 films. As well, all the results acquired in current investigation
such as crystallite size, crystallinity, surface morphology with EDX results and micro-hardness values of
synthesized films with increasing plasma focus shots concur well with prior researches [39, 40].

4. Conclusions

Successful formation of MAS thin films has been attained by using DPF device. The deposition for MgAl2O4 thin
films is achieved by using 5, 10, 15, 20, 30 and 40 plasma focus shots. Structural analysis showed that the
diffraction peaks corresponding to (222), (400) and (622) planes increased for all deposited plasma focus shots.
Whereas (220) and (440) planes of Al substrate are decreased with increase in plasma focus shots. The mean
crystallite size of deposited MgAl2O4 thin films increased upto 20 plasma focus shots and then decreased. The
mean crystallite size ranged from 21.9 to 23.8 nm showing non linear behavior with change in plasma focus
shots. FTIR spectrums showed a major common transmittance band at 697.95 cm−1 which correspond to the
existence of AlO6 groups, building up MgAl2O4 and confirmed the successful growth of MgAl2O4 films. SEM
micrograph showed that with increase in plasma focus shots, surface particles merge to form large agglomerates.
At higher plasma focus shots (30 to 40 focus shots) multi layers with significant melting effects is observed. EDX
results confirmed that magnesium and oxygen contents grow with increasing the number of deposited focus
shots utilized for synthesized film. However greatest concentration of both elements is determined in the
synthesized film with forty (maximum) plasma focus shots. Hardness graph exhibited an increasing behavior in
micro-hardness of MgAl2O4 films by increasing number of plasma focus shots. For forty plasma focus shots, the
micro-hardness of MgAl2O4 film is found to be 1087 MPa which is almost two times the micro-hardness of
untreated aluminum. The structure, morphology, composition and hardness analysis performed for synthesized
thin film of MgAl2O4, exhibited that variation in plasma focus shots has strong effect on MAS thin film
formation.

ORCID iDs

Syed Muhammad Ahmad https://orcid.org/0000-0001-8937-0072

Riaz Ahmad https://orcid.org/0000-0002-8377-6431

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