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: [email protected] (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 X-ray diffractometer with cuka radiation (k = 1.5418 Å) in the
passivation of surfaces against corrosion, and as catalysts [2]. In range of 10–70° in steps of 0.025 at a scan speed 2°/min. High
the emerging field of nanotechnology, a goal is to make nanostruc- resolution transmission electron microscopy (HR-TEM) examined
tures or nanoarrays with special properties with respect to those of were performed using JEOL 4000CX electron microscopes. Bright-
bulk or single particle species [3]. Oxide nanoparticles can exhibit field images and selected area electron diffraction (SAED) patterns
inimitable physical and chemical properties due to their limited were obtained from several zones for each sample to observe the
size and a high density of corner or edge surface sites [4]. The effect morphology and structure. Photoluminescence study using Jobin
of II–VI semiconductor nanocrystals are recently developed class of Yuan F-100 Fulog3-11 spectrofluorometer in the range 200–
nanomaterials whose unique physico-chemical properties are 700 nm. The emission was collected and sent to a Jobin-yuon Triax
helping to create a new generation in the field of nano-photonics monochromator and detected by a Hamamastsu Ra28 photomulti-
and microelectronics [5]. The catalytic behavior of metal oxides plier tube. A Renishaw micro-Raman spectrometer RM 2000 with
may be described in the reaction involved oxidation process [6]. IR (632.8 nm) and UV (325 nm) excitation lasers was employed
The catalytic system of oxide type-catalysts is of particular impor- to measure the non-resonant and resonant Raman spectra of
tance where the active component exists in different oxidation MgO:CuO nanosamples. All AFM images were acquired under tap-
states [7,8]. The coexistence of cations of different valence states ping mode on a Digital Instrument Nanoscope IIIA at ambient con-
in solid catalysts from ion pairs or donor–acceptor sites acting as ditions. A sharp TESP tip (Veeco) with a radius of end of 8 nm was
active sites in the catalytic reactions [9,10]. The catalytic activity used. Typical values for the force constant and resonance frequen-
of oxide catalysts is controlled by sites present in small concentra- cy were 42 N/m and 320 kHz. The confocal microscopic studies
tion on its surface. Other hand, copper oxide (CuO) is one of the were performed on a Olympus-FluoView 1000 B. Electrochemical
metal oxides that are very sensitive to the method of preparation experiments were performed using CHI-760c, USA Potentiostat
and activation conditions [11,12]. Recently the observations on with three electrode single compartment cell setup. Here Pt wire
the optical absorption studies of nanosized MgO:CuO nanopow- and Hg/HgCl2 are used as counter and reference electrode, and
ders indicates that the synthesized MgO is quite suitable for glassy carbon electrode (GCE) as working electrode and all the
adsorption and dissociation of polar molecules, toxic waste reme- potentials were measured vs. GCE. The preparation of the modified
diation, etc. Further it is also noted that the synthesized MgO:CuO electrode is very important because the electrochemical tech-
nanocrystals contains F- and M defect centers, which are responsi- niques one of the most sensitive instruments in trace level detec-
ble for creating energy levels within the band gap (3.8 eV) of MgO tion. The surface of the CGE was polished using 0.3 micron
[13,14]. Kim et al. studied the effect of acetic acid addition to mag- alumina slurry, followed by extensive washed with distilled water.
nesium methoxide on the stability of the precursor and the crystal- For the preparation of MgO/CuO modified GCE (MgO/CuO/GCE),
lization behavior of sol–gel derived MgO nanosize powder [15]. sample amount 1–2 mg were placed on micro slide, making wet
Additionally, Kumar et al. have synthesized MgO with high degree with ethanol and rubbed over the material, causing some amount
of crystallinity and tubular morphology using magnesium acetate of MgO/CuO adhere on the electrode surface and dried.
as a precursor [16]. In the present study, the synthesis and
microstructural characterization of MgO doped and CuO nanopar-
Result and discussions
ticles synthesized by wet-chemical method are discussed.

Experimental section X-ray diffraction analysis

All chemical reagents used in this experiment were of analytical X-ray powder diffraction (XRD) studies were carried out to con-
grade (E-Merck, 99.99%), were procured commercially and were firm the crystallinity using Richseifert X-ray diffractometer with
used without further purification. The starting materials for the cuka radiation (k = 1.5418 Å) in the range of 10–70° in steps of
preparation of MgO doped CuO nanomaterials were synthesized 0.025 at a scan speed 2°/min. The XRD pattern is shown in Fig. 1.
by taking magnesium nitrate [Mg(NO3)2], copper (II) nitrate, The spectrum reflects the good crystallinity for both the pure and
Cu(NO3)2 and glycine [NH2CH2COOH] in the appropriate stoichio- doped MgO nanosamples. The broadness of the XRD peaks indicates
metric ratio. The calculated amount of glycine was first dissolved the nanocrystalline nature of pure and doped MgO:CuO nanoparti-
in deionized water. Mg(NO3)2 and Cu(NO3)2 was then added to cles. The Bragg’s reflections are indexed in MgO like cubic structure
the solution slowly by constant stirring simultaneously, main- and the estimated cell constant a is (a = 4.21 Å) of MgO particles
tained at a temperature of 120 °C. The heating temperature of confirms that the sample is formed in a single phase and this cell
the homogeneous mixture should be mentioned was filtered out constant is slightly less than that of Cu–MgO nanosamples which
using ultra-fine filter paper and heated with an electrical heating may be due to the introduction of copper in MgO (a = 4.46 Å). Con-
mantle for three hours. N2 and CO2 evolved as bright pale yellow siderably broadened lines in the XRD patterns are indicative of the
gas mixture and MgO:CuO was left behind as the end residue. presence of nano-size particles. We have used the (2 0 0) reflection,
The synthesized nanopowders was annealed at 700 °C in a micro- like in the XRD patterns, for obtaining the average particle size
processor controlled single zone furnace for 12 h, thereby resulting with the help of Debye–Scherrer’s equation D = 0.9 k/B cos h,
in a good quality MgO:CuO nanocrystals. When the reaction com- B = (B2M B2S )1/2 where ‘D’ is the thickness (diameter) of the particle,
pleted, the products were filtered and washed with water and k is the X-ray wavelength (1.5418 Å), BM and BS are respectively the
absolute ethanol several times. The final products were collected measured peak broadening and the instrumental broadening in
and once again washed with toluene. Similar experimental proce- radian and ‘h’ is the Bragg angle of the reflection. The calculated
dure was adopted for the synthesis of Cu doped MgO nanocrystals average particle sizes for MgO and Cu. MgO nanosamples were 15
with different molar concentrations. and 30 nm respectively. The XRD pattern of regenerated MgO
powder ascertains MgO and the Cu doped MgO samples.
Characterization studies
HR-TEM and SAED analysis
The powdered samples of magnesium doped copper oxide
nanocrystals were subjected to X-ray powder diffraction (XRD) In order to analyze the structure and morphology of synthe-
analyses were performed at room temperature on a Richseifert sized pure and doped samples. The instrument was accelerated
 K. Kaviyarasu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 142 (2015) 405–409 407

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
Fig. 1. XRD pattern of MgO:CuO nanocrystals.
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
with a voltage of 20 KV and the samples were scanned at a working of the photoluminescence peaks is a result of band gap reduction.
distance of 15 mm. The samples were dispersed in isopropyl alco- Such a characteristic is vital for enhancement of secondary electron
hol and scanned with a magnification of 10,000. The HR-TEM emission efficiency, reduction of flickening, etc. And therefore this
images for the pure and doped samples are shown in Fig. 2(a–d) optical property is promising for its application in plasma display
respectively. The formation of MgO:CuO aggregates consisting of panels (PDP) or other optical fields [21].
very tiny three dimensional (3D) disordered primary nanoparticles
with interplanar connections was observed. The particle size of the Micro-Raman techniques
sample is in the range of approximately 10–30 nm which agrees
well with the crystalline size from the XRD analysis implying that The Raman spectrum of the pure MgO:CuO nanocrystals in the
the synthesized MgO:CuO nanocrystals contain some single crystal 100–3000 cm 1 region was recorded by RENISHAW which is a high
domains with the same oriented crystal plane [17]. It is also clear performance Raman microscope spectrometer using a 632.8 nm
that the synthesized MgO:CuO nanosample is very porous in nat- diode lasers. Fig. 4(a–c) shows the Raman spectra of MgO:CuO
ure and when it is doped with Cu, the porosity increases with pores nanocrystals revealed the distinct peaks at room temperature
and open voids. To considering interplanar distances and geometry (RT). First sharp peak appears at 365 cm 1 which is not existent
of MgO:CuO nanocrystals. The SAED patterns to analysis of the in pure MgO nanocrystals, but when copper is added, it started
crystalline phases obtained after calcinations at room temperature to be observed [22,23]. The area under the Raman peak changed
(RT). The diffraction peaks were very diffuse suggesting that the with the copper percentage and increased with higher concentra-
texture is quite polycrystalline with small grain size. Therefore tion, probably due to copper in induced surface roughness to iden-
the distributed pore sizes and the mean pore diameter obtained tify the PL and AFM images.

Fig. 2. (a–d). HR-TEM & SAED images of MgO:CuO nanocrystals.

408 K. Kaviyarasu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 142 (2015) 405–409

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
Fig. 3. Photoluminescence spectrum of MgO:CuO nanocrystals. 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.
Atomic force microscopic studies The room temperature optical spectra of pure MgO and the Cu
doped magnesium nanosamples are shown in Fig. 6(a and b), shows
Height calibrations were performed using the step heights of the images of magnesium doped copper oxide nanoparticles. The
freshly cleaved MgO:CuO nanosamples. Due to the super-rough- studies indicate that the fluorescence generated by MgO doped
ness of the samples, sometimes the laser interference pattern along CuO nanoparticles shows a change in fluorescence in the solid state
the slow-scan axis was hard to avoid, which is more noticeable in along the vortex region. One intriguing aspect of MgO doped CuO
large-area scanning and has a period of twice the wavelength of nanoparticles is that the domains which define the pattern as
the laser. This is caused by the constructive interference of laser shown in Fig. 6(c), can be made discrete or continuous by lowering
reflected from the sample surface and that reflected from the can- or increasing the dopant concentration in the pure CuO nanopow-
tilever. The nanosamples investigated in this work have been ders. Interestingly the pattern generated by the fluorescent light
obtained by the micromechanical behavior of MgO:CuO nanocrys- could be useful in the applications such as biological marking.
tals were mechanically exfoliated and transferred of this silicon Moreover, the spectrum of our MgO:CuO nanocrystals is different
wafer, which were covered with 100 nm of thermal oxide. We from that of the nanoparticles synthesized by wet-chemical

Fig. 4. (a–c). Micro-Raman spectrum of MgO:CuO nanocrystals.

Fig. 5. (a–c). Atomic force microscopy images of MgO:CuO nanocrystals.

 K. Kaviyarasu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 142 (2015) 405–409 409

Fig. 6. (a–c). Confocal images of MgO:CuO nanocrystals.

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.

Fig. 7. Electrochemical behavior MgO:CuO nanocrystals. References

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