Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 142 (2015) 405–409

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Synthesis and characterization studies of MgO:CuO nanocrystals

by wet-chemical method
K. Kaviyarasu a,d,⇑, C. Maria Magdalane b, K. Anand c, E. Manikandan d, M. Maaza d
a
Department of Physics, Sri Sankara Arts and Science College, Kanchipuram, Tamil Nadu, India
b
Department of Chemistry, St. Xavier’s College (Autonomous), Tirunelveli, Tamil Nadu, India
c
Department of Chemistry, Faculty of Applied Science, Durban University of Technology, Durban, South Africa
d
UNESCO-UNISA AFNET in Nanoscience/Nanotechnology Laboratories, Materials, Research Department and Nanoscience Laboratories, iThemba LABS-National Research Foundation
(NRF) of South Africa, Somerset West, South Africa

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Nanocomposites structures of
MgO:CuO is prepared by wet-
chemical method.
 Optical luminescence and Raman
scattering of MgO:CuO is studied.
 Crystalline and molecular behaviors
of nanocomposite crystals.
 Morphological results ensured the
nanoporous structures of MgO:CuO.
 Opto/electrochemical properties of
MgO:CuO are potential for device
development.

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

Article history: In this report, we examine the progress in adapting these nanomaterials for several predominantly pho-
Received 1 October 2014 tonics device fabrication by wet-chemical method. Nanocomposite of magnesium oxide (MgO) with cop-
Received in revised form 16 December 2014 per oxide (CuO) doped nanoparticles were characterized by X-ray powder diffraction (XRD) and the
Accepted 30 January 2015
observed peaks are quite agreeable with the pure phase cubic structure. High-resolution transmission
Available online 7 February 2015
electron microscopic (HR-TEM) results reveal that the resultant nanopowders are porous and agglomer-
ated with polycrystalline nano-entities. Field emission of selected-area electron diffraction (SAED) stud-
Keywords:
ies showed that the average size of the nanoparticles were 20 nm. Photoluminescence spectra of
Nanocomposites
Microstructure
MgO:CuO were investigated, showing emission peaks around 375 nm relating to new energy levels
Optical characterization induced by defects or defect levels generation and confocal micro-Raman images indicated that the che-
X-ray techniques mical molecular vibrational band structure and morphology of the product which is spherical shaped
Electrical characterization nanoparticles with an average particle size of 25 nm with standard deviation. The electrochemical
response of MgO:CuO which is proves that the nano-copper/magnesium has high functionality due to
the small size and it has higher electrochemical activity without any modifications.
Ó 2015 Published by Elsevier B.V.

Introduction

Nanoparticles of transition conducting metal oxides (TCMOs)

have been investigated by several workers in the last few years.
⇑ Corresponding author at: Department of Physics, Sri Sankara Arts and Science Besides their structural aspects, optical properties of the oxide
College, Kanchipuram, Tamil Nadu, India. Tel.: +91 9042170870. nanoparticles are of particular interest [1]. In technological
E-mail address: kaviyarasuloyolacollege@gmail.com (K. Kaviyarasu). applications, oxides are used in the fabrication of microelectronic

http://dx.doi.org/10.1016/j.saa.2015.01.111
1386-1425/Ó 2015 Published by Elsevier B.V.
406 K. Kaviyarasu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 142 (2015) 405–409
circuits, sensors, piezoelectric devices, fuel cells, coatings for the
passivation of surfaces against corrosion, and as catalysts [2]. In
the emerging field of nanotechnology, a goal is to make nanostruc-
tures or nanoarrays with special properties with respect to those of
bulk or single particle species [3]. Oxide nanoparticles can exhibit
inimitable physical and chemical properties due to their limited
size and a high density of corner or edge surface sites [4]. The effect
of II–VI semiconductor nanocrystals are recently developed class of
nanomaterials whose unique physico-chemical properties are
helping to create a new generation in the field of nano-photonics
and microelectronics [5]. The catalytic behavior of metal oxides
may be described in the reaction involved oxidation process [6].
The catalytic system of oxide type-catalysts is of particular impor-
tance where the active component exists in different oxidation
states [7,8]. The coexistence of cations of different valence states
in solid catalysts from ion pairs or donor–acceptor sites acting as
active sites in the catalytic reactions [9,10]. The catalytic activity
of oxide catalysts is controlled by sites present in small concentra-
tion on its surface. Other hand, copper oxide (CuO) is one of the
metal oxides that are very sensitive to the method of preparation
and activation conditions [11,12]. Recently the observations on
the optical absorption studies of nanosized MgO:CuO nanopow-
ders indicates that the synthesized MgO is quite suitable for
adsorption and dissociation of polar molecules, toxic waste reme-
diation, etc. Further it is also noted that the synthesized MgO:CuO
nanocrystals contains F- and M defect centers, which are responsi-
ble for creating energy levels within the band gap (3.8 eV) of MgO
[13,14]. Kim et al. studied the effect of acetic acid addition to mag-
nesium methoxide on the stability of the precursor and the crystal-
lization behavior of sol–gel derived MgO nanosize powder [15].
Additionally, Kumar et al. have synthesized MgO with high degree
of crystallinity and tubular morphology using magnesium acetate
as a precursor [16]. In the present study, the synthesis and
microstructural characterization of MgO doped and CuO nanopar-
ticles synthesized by wet-chemical method are discussed.
Experimental section
All chemical reagents used in this experiment were of analytical
grade (E-Merck, 99.99%), were procured commercially and were
used without further purification. The starting materials for the
preparation of MgO doped CuO nanomaterials were synthesized
by taking magnesium nitrate [Mg(NO3)2], copper (II) nitrate,
Cu(NO3)2 and glycine [NH2CH2COOH] in the appropriate stoichio-
metric ratio. The calculated amount of glycine was first dissolved
in deionized water. Mg(NO3)2 and Cu(NO3)2 was then added to
the solution slowly by constant stirring simultaneously, main-
tained at a temperature of 120 °C. The heating temperature of
the homogeneous mixture should be mentioned was filtered out
using ultra-fine filter paper and heated with an electrical heating
mantle for three hours. N2 and CO2 evolved as bright pale yellow
gas mixture and MgO:CuO was left behind as the end residue.
The synthesized nanopowders was annealed at 700 °C in a micro-
processor controlled single zone furnace for 12 h, thereby resulting
in a good quality MgO:CuO nanocrystals. When the reaction com-
pleted, the products were filtered and washed with water and
absolute ethanol several times. The final products were collected
and once again washed with toluene. Similar experimental proce-
dure was adopted for the synthesis of Cu doped MgO nanocrystals
with different molar concentrations.
Characterization studies
The powdered samples of magnesium doped copper oxide
nanocrystals were subjected to X-ray powder diffraction (XRD)
analyses were performed at room temperature on a Richseifert
X-ray diffractometer with cuka radiation (k = 1.5418 Å) in the
range of 10–70° in steps of 0.025 at a scan speed 2°/min. High
resolution transmission electron microscopy (HR-TEM) examined
were performed using JEOL 4000CX electron microscopes. Bright-
field images and selected area electron diffraction (SAED) patterns
were obtained from several zones for each sample to observe the
morphology and structure. Photoluminescence study using Jobin
Yuan F-100 Fulog3-11 spectrofluorometer in the range 200–
700 nm. The emission was collected and sent to a Jobin-yuon Triax
monochromator and detected by a Hamamastsu Ra28 photomulti-
plier tube. A Renishaw micro-Raman spectrometer RM 2000 with
IR (632.8 nm) and UV (325 nm) excitation lasers was employed
to measure the non-resonant and resonant Raman spectra of
MgO:CuO nanosamples. All AFM images were acquired under tap-
ping mode on a Digital Instrument Nanoscope IIIA at ambient con-
ditions. A sharp TESP tip (Veeco) with a radius of end of 8 nm was
used. Typical values for the force constant and resonance frequen-
cy were 42 N/m and 320 kHz. The confocal microscopic studies
were performed on a Olympus-FluoView 1000 B. Electrochemical
experiments were performed using CHI-760c, USA Potentiostat
with three electrode single compartment cell setup. Here Pt wire
and Hg/HgCl2 are used as counter and reference electrode, and
glassy carbon electrode (GCE) as working electrode and all the
potentials were measured vs. GCE. The preparation of the modified
electrode is very important because the electrochemical tech-
niques one of the most sensitive instruments in trace level detec-
tion. The surface of the CGE was polished using 0.3 micron
alumina slurry, followed by extensive washed with distilled water.
For the preparation of MgO/CuO modified GCE (MgO/CuO/GCE),
sample amount 1–2 mg were placed on micro slide, making wet
with ethanol and rubbed over the material, causing some amount
of MgO/CuO adhere on the electrode surface and dried.
Result and discussions
X-ray diffraction analysis
X-ray powder diffraction (XRD) studies were carried out to con-
firm the crystallinity using Richseifert X-ray diffractometer with
cuka radiation (k = 1.5418 Å) in the range of 10–70° in steps of
0.025 at a scan speed 2°/min. The XRD pattern is shown in Fig. 1.
The spectrum reflects the good crystallinity for both the pure and
doped MgO nanosamples. The broadness of the XRD peaks indicates
the nanocrystalline nature of pure and doped MgO:CuO nanoparti-
cles. The Bragg’s reflections are indexed in MgO like cubic structure
and the estimated cell constant a is (a = 4.21 Å) of MgO particles
confirms that the sample is formed in a single phase and this cell
constant is slightly less than that of Cu–MgO nanosamples which
may be due to the introduction of copper in MgO (a = 4.46 Å). Con-
siderably broadened lines in the XRD patterns are indicative of the
presence of nano-size particles. We have used the (2 0 0) reflection,
like in the XRD patterns, for obtaining the average particle size
with the help of Debye–Scherrer’s equation D = 0.9 k/B cos h,
B = (B2M B2S )1/2 where ‘D’ is the thickness (diameter) of the particle,
k is the X-ray wavelength (1.5418 Å), BM and BS are respectively the
measured peak broadening and the instrumental broadening in
radian and ‘h’ is the Bragg angle of the reflection. The calculated
average particle sizes for MgO and Cu. MgO nanosamples were 15
and 30 nm respectively. The XRD pattern of regenerated MgO
powder ascertains MgO and the Cu doped MgO samples.
HR-TEM and SAED analysis
In order to analyze the structure and morphology of synthe-
sized pure and doped samples. The instrument was accelerated
 K. Kaviyarasu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 142 (2015) 405–409
Fig. 1. XRD pattern of MgO:CuO nanocrystals.
with a voltage of 20 KV and the samples were scanned at a working
distance of 15 mm. The samples were dispersed in isopropyl alco-
hol and scanned with a magnification of 10,000. The HR-TEM
images for the pure and doped samples are shown in Fig. 2(a–d)
respectively. The formation of MgO:CuO aggregates consisting of
very tiny three dimensional (3D) disordered primary nanoparticles
with interplanar connections was observed. The particle size of the
sample is in the range of approximately 10–30 nm which agrees
well with the crystalline size from the XRD analysis implying that
the synthesized MgO:CuO nanocrystals contain some single crystal
domains with the same oriented crystal plane [17]. It is also clear
that the synthesized MgO:CuO nanosample is very porous in nat-
ure and when it is doped with Cu, the porosity increases with pores
and open voids. To considering interplanar distances and geometry
of MgO:CuO nanocrystals. The SAED patterns to analysis of the
crystalline phases obtained after calcinations at room temperature
(RT). The diffraction peaks were very diffuse suggesting that the
texture is quite polycrystalline with small grain size. Therefore
the distributed pore sizes and the mean pore diameter obtained
Fig. 2. (a–d). HR-TEM & SAED images of MgO:CuO nanocrystals.
407
from the N2 adsorption–desorption analysis would represent the
exact values of the whole samples [18].
Photoluminescence studies
The photoluminescence studies are carried out to detect the
lower concentration of defects rather than the optical absorption.
This is a mechanism where the impurity on absorption of light,
gives rise to the bound excited state from which it returns to its
ground state abiding in accordance with the color center creation
mechanism [19]. The room temperature photoluminescence spec-
tra of MgO:CuO nanosamples are shown in Fig. 3. When the exci-
tation wavelength is 250 nm, for peaks are observed at 345, 365
and 375 nm respectively. The peak at 365 nm can be attributed
to the relaxation of polarization defects formed by the strained
sites attached to oxygen vacancies. Oxygen vacancy which might
be the common defect in the nanosamples induces distortion of
the lattice in its direct surrounding. In the case of samples, the
red shift in the MgO is slightly enhanced [20]. Therefore, red shift
of the photoluminescence peaks is a result of band gap reduction.
Such a characteristic is vital for enhancement of secondary electron
emission efficiency, reduction of flickening, etc. And therefore this
optical property is promising for its application in plasma display
panels (PDP) or other optical fields [21].
Micro-Raman techniques
The Raman spectrum of the pure MgO:CuO nanocrystals in the
100–3000 cm 1 region was recorded by RENISHAW which is a high
performance Raman microscope spectrometer using a 632.8 nm
diode lasers. Fig. 4(a–c) shows the Raman spectra of MgO:CuO
nanocrystals revealed the distinct peaks at room temperature
(RT). First sharp peak appears at 365 cm 1 which is not existent
in pure MgO nanocrystals, but when copper is added, it started
to be observed [22,23]. The area under the Raman peak changed
with the copper percentage and increased with higher concentra-
tion, probably due to copper in induced surface roughness to iden-
tify the PL and AFM images.
408 K. Kaviyarasu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 142 (2015) 405–409
Fig. 3. Photoluminescence spectrum of MgO:CuO nanocrystals.
Atomic force microscopic studies
Height calibrations were performed using the step heights of
freshly cleaved MgO:CuO nanosamples. Due to the super-rough-
ness of the samples, sometimes the laser interference pattern along
the slow-scan axis was hard to avoid, which is more noticeable in
large-area scanning and has a period of twice the wavelength of
the laser. This is caused by the constructive interference of laser
reflected from the sample surface and that reflected from the can-
tilever. The nanosamples investigated in this work have been
obtained by the micromechanical behavior of MgO:CuO nanocrys-
tals were mechanically exfoliated and transferred of this silicon
wafer, which were covered with 100 nm of thermal oxide. We
Fig. 4. (a–c). Micro-Raman spectrum of MgO:CuO nanocrystals.
Fig. 5. (a–c). Atomic force microscopy images of MgO:CuO nanocrystals.
identified the single- and spherical shaped by the color influence
in the optical microscope, the MgO:CuO nanocrystals were imaged
by the atomic force microscopy (AFM) to ensure the uniformity of
the surface layer. Fig. 5(a–c) shows a typical AFM image of the
MgO:CuO nanolayers on a silicon substrate, which were used for
this study. After AFM quality control, the MgO:CuO nanocrystals
on silicon substrates were transferred under the optical micro-
scope connected to the Raman spectrometer (Fig. 6 shows the actu-
al spots from which the Raman data were collected). To confirm
this finding, Raman spectroscopic mapping was performed on large
surface nanocrystals before and after at RT.
Confocal microscopic studies
The polarization dependence and the effect of fluorescence of
pure and magnesium doped copper oxide nanoparticles were visu-
alized by confocal laser scanning microscopic studies. This is a
mechanism where the impurity on absorption of light, gives rise
to the bound excited state from which it returns to its ground state
abiding in accordance with the color center creation mechanism.
The room temperature optical spectra of pure MgO and the Cu
doped magnesium nanosamples are shown in Fig. 6(a and b), shows
the images of magnesium doped copper oxide nanoparticles. The
studies indicate that the fluorescence generated by MgO doped
CuO nanoparticles shows a change in fluorescence in the solid state
along the vortex region. One intriguing aspect of MgO doped CuO
nanoparticles is that the domains which define the pattern as
shown in Fig. 6(c), can be made discrete or continuous by lowering
or increasing the dopant concentration in the pure CuO nanopow-
ders. Interestingly the pattern generated by the fluorescent light
could be useful in the applications such as biological marking.
Moreover, the spectrum of our MgO:CuO nanocrystals is different
from that of the nanoparticles synthesized by wet-chemical
 K. Kaviyarasu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 142 (2015) 405–409
Fig. 6. (a–c). Confocal images of MgO:CuO nanocrystals.
Fig. 7. Electrochemical behavior MgO:CuO nanocrystals.
method which shows the band broadening with decrease in inten-
sity. This difference can be attributed to the effect of smaller parti-
cle size, which affects the force constant and vibrational amplitudes
of the nearest neighboring bond. In this present samples were ana-
lyzed by 514.5 nm Ar+ excitation source respectively [24].
Electrochemical behavior of MgO/CuO
Fig. 7 shows the electrochemical responses of the MgO/CuO/
GCE were studied using cyclic voltammogram (CV) in 0.1 M NaOH
as electrolyte at scan rate (50 mV/s) in the potential range 1.0 V–
1.0 V. Fig. 7 shows three couple of redox responses clearly in the
slow scan rate (20 mV). Three peaks are observed in the anodic
sweep at 0.22 V, 0.13 V and +0.1 V (A1, A2 & A3) which is
attributed to the oxide formation of Cu to Cu2O, Cu2O to CuO and
CuO to Cu(OH)2, respectively. The observed other three peaks in
the cathodic sweep at 0.16 V, 0.31 V and 0.84 V (C1, C2 & C3)
are the corresponding cathodic reduction of peaks (A1, A2 & A3).
In this case, the different form of Cu(II) oxides has predominant
character than the magnesium oxide due to its redox properties
which confirm by the observed responses. Because the reductive
charges of copper are always higher than the oxidative charges
so the broad peaks are observed and also it is semiconducting
materials which is observed predominant responses in CV analysis
[25]. Fig. 7 shows the multi scan spectra, which indicates the MgO/
CuO/GCE has higher redox properties by the increasing current in
every segments at cupric and cuprous oxide but in the hydroxide
409
region the current was decreased in hydroxide response due to
its adsorption of solid interfacial layer on the MgO/CuO/GCE.
Conclusions
In this study, a wet-chemical method to prepare high quality
MgO and Cu doped magnesium nanocrystals, has been achieved.
It is safer, easier to perform, and more cost effective with the
XRD data indicate that MgO and CuO doped magnesium nanopar-
ticles exhibit lesser defective crystalline internal perfection. The
structural perfection and the growth features of the synthesized
crystals were studied. The quality of the nanocrystals was visual-
ized by observing the surface morphology using HR-TEM studies.
The control on size and size distribution were demonstrated by
HR-TEM results. Owing to all these properties the synthesized
nanocrystals could be promising materials for modern materials
design.
References
[1] P.D. Yang, C.M. Lieber, Science 273 (1996) 1836.
[2] A. Bhargava, J.A. Alarco, I.D. Mackinnon, D. Page, A. Liyushechkin, Mater. Lett.
34 (1998) 133.
[3] B.M. Choudry, R.S. Mulukutla, K.J. Klabunde, J. Am. Chem. Soc. 125 (2003) 2020.
[4] K. Kaviyarasu, D. Sajan, M.S. Selvakumar, S. Augustine-Thomas, D. Prem-
Anand, J. Phys. Chem. Sol. 73 (2012) 1396.
[5] K. Kaviyarasu, D. Prem Anand, S. Stanly John Xavier, S. Augustine Thomas, S.
Selvakumar, J. Mater. Sci. Technol. 28 (2012) 15.
[6] C.B. Roy, J. Catal. 12 (1968) 129.
[7] J.R. Goldstein, A.C. Tseung, J. Catal. 33 (1974) 452.
[8] R.N. Ram, B.B. Prasad, Z. Phys. Chem. 259 (1978) 1169.
[9] R.B. Fahim, M.I. Zaki, R.M. Gabr, Powder Technol. 30 (1981) 161.
[10] G.A. El-shobaky, N.E. Radwan, F.M. Radwan, Adsorpt. Sci. Technol. 16 (1998)
733.
[11] P. Lahiri, S.K. Sengupta, Can. J. Chem. 69 (1991) 33.
[12] V. Mucka, Collect. Czech. Chem. Commun. 42 (1977) 2074.
[13] Y.D. Li, M. Sui, Y. Ding, G. Zhang, J. Zhuang, C. Wang, Adv. Mater. 12 (2000) 818.
[14] M.S. Melgunov, V.B. Fenelonov, E.A. Melgunova, J. Phys. Chem. 107 (2003)
2427.
[15] J.Y. Kim, H.S. Jung, K.S. Hong, J. Am. Ceram. 88 (2005) 784.
[16] A. Kumar, J. Kumar, J Phys. Chem. Sol. 69 (2008) 2764.
[17] A.J. Moodie, C.E. Warble, J. Cryst. Growth 74 (1986) 89.
[18] I.F. Guilliatt, N.H. Brett, Trans. Br. Ceram. Soc. 69 (1970) 127.
[19] K. Kaviyarasu, D. Premanand, J. Kennedy, E. Manikandan, Int. J. Nanosci. 12
(2013) 1350033.
[20] K. Kaviyarasu, E. Manikandan, P. Paulraj, S.B. Mohamed, J. Kennedy, J. Alloys
Compd. 593 (2014) 67.
[21] T.D. Chen, T.G. Stoebe, Radiat. Prot. Dosim. 78 (1998) 101.
[22] S. Puppalwar, S. Dhoble, N. Dhoble, A. Kumar, Nucl. Instrum. Meth. B 274
(2012) 167.
[23] H. Aboud, H. Wagiran, I. Hossain, R. Hussin, Int. J. Phys. Sci. 7 (2012) 929.
[24] K. Kaviyarasu, D. Sajan, M.S. Selvakumar, S. Augustine-Thomas, D. Prem-
Anand, J. Phys. Chem. Solids 73 (2012) 1400.
[25] B. Khalilzadeh, M. Hasanzadeh, S. Sanati, L. Saghatforoush, N. Shadjou, E.N.
Jafar, P. Dolatabadi, Int. J. Electrochem. Sci. 6 (2011) 4175.