Optik 127 (2016) 2360–2365

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Optik
journal homepage: www.elsevier.de/ijleo

Microwave-assisted synthesis, characterization and antibacterial

properties of Ce–Cu dual doped ZnO nanostructures
J. Arul Mary a , J. Judith Vijaya a,∗ , L. John Kennedy b , M. Bououdina c,d
a
Catalysis and Nanomaterials Research Laboratory, Department of Chemistry, Loyola College, Chennai 600 034, India
b
Materials Division, School of Advanced Sciences, Vellore Institute of Technology (VIT) University, Chennai Campus, Chennai 600 127, India
c
Nanotechnology Centre, University of Bahrain, PO Box 32038, Bahrain
d
Department of Physics, College of Science, University of Bahrain, PO Box 32038, Bahrain

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

Article history: In this paper, a simple and proficient approach of one-pot design of Ce and Cu dual doped nanostructures
Received 3 March 2015 was obtained via microwave assisted combustion method. A number of analytical techniques, comprising
Accepted 2 November 2015 X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX)
and photoluminescence spectroscopy (PL) have been employed to characterize the as prepared samples.
Keywords: XRD analysis revealed that the dual-doped ZnO nanostructures are of wurtzite crystal structure. The
Optical properties
variation in lattice parameters, micro-strain and a minor shift in XRD peaks endorses the substitution of
Microwave combustion
co dopants into the ZnO lattice. SEM investigations exhibited that the samples are of irregular spherical
Grain size
ZnO
and hexagonal morphology. DRS measurements showed a decline in the bandgap with increasing dopants
Antibacterial activity content, perhaps due to an increase in the lattice parameters. PL probe of the samples showed the violet,
blue and green peaks for the samples. The antibacterial property test carried out via well diffusion method,
revealed the higher antimicrobial activity of the samples. Thus, the as-synthesized sample showed is an
economically and environmentally friendly nanostructure.
© 2015 Elsevier GmbH. All rights reserved.

1. Introduction antibacterial properties. Currently, ZnO nanostructures are used

At present, human race is going through various danger-
ous threats from harmful bacteria, viruses, fungi and other
microorganisms [1]. Well-being and environmental concerns have
progressively become the centre of attention all over the world. The
utilization of antibacterial agents to prevent or destroy harmful
bacteria is one of the vital resources to advance in environmen-
tal hygiene and human well-being [2]. As of now, nanostructured
materials pose encouraging prospects as antibacterial agents, due
to their unique physicochemical properties, caused by their nano-
sized dimensions and large surface/volume ratios [3]. They are less
toxic, exhibit greater selectivity, superior durability, heat resis-
tance and chemical stability. Metal oxides nanostructures would
play a vital role in biomedical sector, due to their incredible
properties at nanoscale, such as, optical, catalytical and antibac-
terial properties. Nano metal oxides, such as TiO2 [4], ZnO, MgO
[5], CuO [6], SiO2 [7], and SnO2 [8] have exhibited significant
∗ Corresponding author. Tel.: +91 44 28178200; fax: +91 44 28175566.
E-mail addresses: jjvijayaloyola@yahoo.co.in, jjvijaya78@gmail.com
(J. Judith Vijaya).
in healthcare products, due to UV blocking capability, high pho-
tocatalytic activity and wide range of antibacterial activity towards
both Gram-positive and Gram-negative bacteria and cost effec-
tive. As an efficient antibacterial agent, ZnO nanostructure are
utilized in food preservation and packaging systems, medical and
skin coatings, water purification, bio-imaging and drug deliv-
ery.
Nowadays, synthesis and applications of ZnO nanostructures
are exceedingly looked-for, due to their fabulous optical, electri-
cal, catalytic and biomedical properties [9] Resistance of bacteria
to antibiotics is gradually rising and drawing great deal of atten-
tion. Significant number of antibiotics has confirmed resistance by
one or another bacterium [10]. These resistant bacteria are fore-
most apprehension for civic health concerns worldwide, which
calls for advanced antibacterial agents [11]. ZnO nanostructures
demonstrate the durable antibacterial activities on a broad spec-
trum of bacteria [12]. The mechanism of antibacterial activity of
ZnO nanostructures is yet under investigation. Amornpitoksuk et al.
[13] ascribed the mechanism to the generation of reactive oxygen
species from ZnO material, which terminates the outer membrane
of bacteria. The rate of production of these surface oxygen species
is greatly increased in doped ZnO. However, recently, Huh et al.

http://dx.doi.org/10.1016/j.ijleo.2015.11.019
0030-4026/© 2015 Elsevier GmbH. All rights reserved.
 J. Arul Mary et al. / Optik 127 (2016) 2360–2365
[14] reported that the antibacterial mechanism of the nanomateri-
als depends on the photocatalytic generation of reactive oxygen
species, which harm the cellular and viral components, disrup-
tion of energy transduction and prevention of enzyme activity and
DNA synthesis. With the intention to improve the effect of these
parameters, the foreign ions are doped in ZnO crystal structure.
A wide range of manufacture paths have been testified for the
synthesis of metal oxide nanoparticles, such as, thermal decompo-
sition, laser ablation, microwave irradiation, sonochemical, reverse
micelles process, chemical reduction, ultrasonic irradiation, radi-
olysis, solvothermal and electrochemical methods [15]. However,
recently microwave-assisted method has been applied in the acti-
vation of clays and synthesis of nanomaterials [16]. Studies have
shown that this method to be an attractive choice to promote the
reactions and is energy effective in heating compared to conven-
tional heat conduction methods, due to the direct heating of the
reaction mixture [17]. In reality, microwave heating is a trans-
fer of electromagnetic energy to thermal energy, and is an energy
transformation phenomenon rather than simple heat transfer [18].
Moreover, the method displays a diminished reaction time, yield
enhancement, small particle size, homogenous and narrow particle
size distribution, high purity materials, and enhanced physico-
chemical properties.
To the best of our literature information, the scientific work of
ours represents the foremost exploration of the antibacterial activ-
ity of the Ce and Cu dual-doped ZnO synthesized using the fast and
efficient microwave combustion method. Therefore, in this paper,
ZnO nanostructures doped with varying amount of Ce and Cu have
been synthesized by microwave combustion method. The physi-
cal properties and antibacterial activity of the samples have been
investigated in detail.
2. Materials and methods
2.1. Synthesis of nanostructures
All the chemicals employed in this investigation were of analyt-
ical grade obtained from Merck, India and were used as obtained
without additional purification. Zinc nitrate (Zn(NO3 )2 ·6H2 O,
98%), cerium nitrate (Ce(NO3 )2 ·6H2 O, 98%), copper nitrate
(Cu(NO3 )2 ·6H2 O, 98%) and urea as a fuel were utilized in this
method. ZnO powders were prepared with the addition of copper
(Cu) and cerium (Ce) of different molar ratios ((Zn1−2x Cex Cux ) O
with x = 0.00, 0.01, 0.02, 0.03, 0.04 and 0.05 to ZnO. The precursor
mixture in urea is dissolved in de-ionized water by using magnetic
stirrer for 30 min and then decanted into a crucible. Later, the cru-
cible is positioned into a microwave oven operating at 800 W for
8 min until the precursor solution mixture decomposes. The solu-
tion at first boils, and then undergoes dehydration, followed by
decomposition with the evolution of large fumes in the form of a
smoke. When the solution reaches the point of spontaneous com-
bustion, it begins to release heat by burning and turns into a solid
powder.
The following chemical reaction takes place during the synthe-
sis,
Urea
Zn(NO3 )2 + Ce(NO3 )2 + Cu(NO3 )2 −→ (Zn1−2x Cex Cux )O
Water
+ gaseous products
The obtained solid powder is washed with ethanol [19], dried
in an oven at 100 ◦ C for 1 h and then annealed at 600 ◦ C for 2 h. The
samples were labelled as follows: undoped sample as pure ZnO,
dual doped samples as ZnCC1, ZnCC2, ZnCC3, ZnCC4, and ZnCC5.
2361
100 002
101
102 110 103 200
f
e
d
Intensity (a.u)
c
b
a
30 35 40 45 50 55 60 65 70
2 Theta (degree)
Fig. 1. XRD patterns of (Zn1−2x Cex Cux ) O (a) Pure ZnO, (b) ZnCC1, (c) ZnCC2, (d)
ZnCC3, (e) ZnCC4, (f) ZnCC5.
2.2. Characterizations
Structural characterization of pure and Ce, Cu dual-doped ZnO
was executed using Rigaku Ultima IV high resolution X-ray diffrac-
tometer (XRD) with CuK␣ radiation ( = 1.5418 Å). Morphological
studies and energy dispersive X-ray analysis have been accom-
plished with a Jeol JSM6360 high-resolution scanning electron
microscope (HR-SEM) equipped with energy dispersive X-ray anal-
ysis (EDX) for elemental chemical analysis. UV–visible diffuse
reflectance spectrum (DRS) was recorded using Cary100 UV–visible
spectrophotometer to estimate the energy band gap. The photolu-
minescence (PL) properties were studied using Varian Cary Eclipse
fluorescence spectrophotometer.
2.3. Determination of antibacterial activity
Antibacterial activity of the prepared nanostructures was
scrutinized towards clinically isolated; Gram-negative Pseu-
domonas aeruginosa, Escherichia coli and Gram-positive Staphylo-
coccus aureus, Klebsiella pneumonia and Bacillus subtilis bacterial
pathogens for in vitro antimicrobial activity. These selected
pathogenic strains were obtained from microbiological division,
Chennai, India.
The antibacterial activity was determined by well diffusion
method. About 25 mL of molten Mueller Hinton Agar was poured
into a sterile Petri plate (Himedia, Mumbai, India). The plates were
allowed to solidify, after which 18 h grown (OD adjusted 0.6) 100 ␮l
of above said pathogenic bacteria cultures were transferred onto
the plate and made culture lawn by using sterile L-rod spreader.
After 5 min setting of the bacteria, the wells were made using ster-
ile 5 mm cork borer and the test samples were dissolved in sterile
water at various concentrations (i.e. 25, 50, 75 and 100 ␮l/well).
The sterile water served as control. The plates were incubated at
37 ◦ C in a 40 W fluorescent light source (∼400 nm) for 24 h. The
antibacterial activity was determined by measuring the diameter
of the zone of inhibition around the well using antibiotic zone scale
in millimetre (mm) (Himedia, Mumbai, India).
3. Results and discussion
3.1. XRD analysis
Fig. 1 displays the characteristic XRD pattern of ((Zn1−2x Cex Cux )
O (x = 0.00, 0.01, 0.02, 0.03, 0.04 and 0.05) nanostructures.
(Zn1−2x Cex Cux ) O nanostructures are crystalline with the sharp
peaks corresponding to the positions 31.73 (100), 34.37 (002), 36.21
2362
Intensity (a.u)
36 37
2 Theta (degree)
Fig. 2. The centre of the most intense peak (002).
(101), 47.48 (102), 56.53 (110), 62.77 (103), 66.30 (200), 67.86 (112)
and 69.00 (201) respectively. The peaks are indexed to the hexago-
nal wurtzite structure of ZnO (JCPDS card No. 89-1397). It is obvious
from the XRD spectra that there are no additional peaks corre-
sponding to the oxides of Ce/Cu or Ce/Cu related secondary and
impurity phases. Fig. 2 indicates that the centre of the most intense
peaks (101) have some extent reallocated towards larger diffracted
angles, and is ascribed to the alteration in the ionic radii of Ce3+ and
Cu2+ ions as compared to that of Zn2+ . Naturally, with the increase
of Cu and Ce content, the XRD peaks of doped samples have con-
stantly decreased in the intensity in comparison to that of pure ZnO.
It is previously reported that the intensity of the diffraction peaks
decrease with an increase in Ce and Cu concentration as compared
to that of undoped ZnO [20–23]. The crystalline size of the prepared
nanostructures was estimated by using Scherrer’s formula,
0.89
L=
ˇ cos 
Fig. 3. HR-SEM images of (Zn1−2x Cex Cux ) O (a) Pure ZnO, (b) ZnCC1, (c) ZnCC3, (d) ZnCC5.
J. Arul Mary et al. / Optik 127 (2016) 2360–2365
where L is the crystallite size, , the X-ray wavelength, , the Bragg
diffraction angle and ˇ, the full width at half maximum (FWHM).
The crystallite size of the samples was found to be 35.36, 38.01,
40.18, 43.55, 46.02 and 46.48 nm respectively. The crystallite size
increases marginally with an increase in the amount of cerium and
copper loading. The presence of co-dopants Ce and Cu in this man-
ner increases the molecular concentration at the crystal surface,
which results in improving the grain growth [24]. The results in
Table 1 reveal that the average size of the crystals increased with
an increase in the concentration of the dopants. This indicates that
the increase in the doping concentration enhances the crystallinity,
which may be attributed to the difference in the ionic radii of
zinc, cerium and iron (Zn2+ = 0.074 nm, Ce3+ = 0.103 nm and Cu2+
(0.072 nm). The volume of unit cell of a hexagonal system has been
calculated from the equation [25].
Volume = (V) 0.866 × a2 × c (2)
The results in Table 1 suggest that the unit cell volume and the
crystallites size vary slightly, thus, confirming the incorporation of
both Ce and Cu ions within ZnO host lattice.
3.2. Scanning electron microscopy (SEM) observations
The HRSEM micrographs of the nanostructures synthesized by
microwave combustion are shown in Fig. 3. Fig. 3(a) exhibits the
hexagonal platforms like morphology for undoped ZnO. Similar
result has also been reported [26]. The average size of the pure
ZnO and co-doped ZnO nanostructures are in nanometer size,
which is evident from the HRSEM pictures. When the co dopant
concentrations were increased from 0.01 to 0.05 M, the grains
shape are converted from hexagonal to spherical shape with the
same wurtzite structure. The particle size of the Ce Cu co-doped
ZnO samples decreased with an increase in the concentration of
(1)
copper and cerium. It has also been observed that when doping
 J. Arul Mary et al. / Optik 127 (2016) 2360–2365 2363

Table 1
Crystallite size (Scherer formula), lattice parameter, cell volume and band gap values of Zn1−2x Cex Cux O (x = 0.00, 0.01, 0.02, 0.03, 0.04 and 0.05) system.

Samples Crystallite size (nm) Lattice Strain (%) Cell volume

parameters (Å) (Å3 )
Scherrer formula Band gap (eV)

Pure ZnO 35.36 3.24 a = 3.2509 0.020 47.56

c = 5.2076
ZnCC 1 38.01 3.19 a = 3.2503 0.025 47.61
c = 5.2049
ZnCC 2 40.18 3.17 a = 3.2511 0.034 47.65
c = 5.2065
ZnCC 3 43.55 3.13 a = 3.2504 0.037 47.64
c = 5.2072
ZnCC 4 46.02 3.11 a = 3.2510 0.049 47.65
c = 5.2061
ZnCC 5 46.48 3.09 a = 3.2511 0.057 47.65
c = 5.2061

concentration increases the particles size decreases from 37 to

10 nm, which is smaller than the pure ZnO and samples becomes
denser. Therefore, HRSEM images show that the surface morphol-
ogy depends upon the concentration of co dopant.

3.3. Energy dispersive X-ray (EDX) analysis

The chemical compositional analysis of the pure and dual doped

ZnO nanostructures was carried out using EDX. The EDX spectra of
pure and Ce, Cu co-doped (Zn1−2x Cex Cux ) O system (x = 0.00, 0.01,
0.02, 0.03, 0.04 and 0.05) are displayed in Fig. 4(a–d). Fig. 4(a) shows
that the Zn and O elements are present in pure ZnO and Fig. 4(b–d)
shows that Zn, Ce, Cu and O elements are contained in doped
(Zn1−2x Cex Cux ) O samples. The EDX analysis affirms the presence of
Ce and Cu in the ZnO system and wt.% is very nearly equal to their
nominal stoichiometry within the experimental error. Therefore,
the EDX spectra show the healthy agreement with the experimental
concentration used for (Zn1−2x Cex Cux ) O system.

3.4. Optical properties (diffuse reflectance spectroscopy)

The optical properties of nanostructures are examined by

UV–visible diffuse reflectance spectroscopy (DRS). Fig. 5(a–f) illus-
trates the band gap energies of the Ce, Cu dual-doped ZnO samples,
which were assessed from the diffuse-reflectance spectra using the
Kubelka–Munk function F(R) [27], and is obtained from the follow-
ing equation,

(1 − R)2
F(R) = (3)
2R

where R is the reflectance. A graph was plotted between [F(R)h]2

and h, and the intercept value is the band gap energy of the
respective sample. The determined values of the band gap of
(Zn1−2x Cex Cux ) O (x = 0.00, 0.01, 0.02, 0.03, 0.04 and 0.05) system
are 3.22, 3.14, 3.12, 3.11, 3.08 and 3.06 eV, respectively. A slight
Fig. 4. EDX spectra of (Zn1−2x Cex Cux ) O (a) ZnCC1, (b) ZnCC3, and, (c) ZnCC5. The
decrease in the optical band gap of the nanostructures is observed inset shows the quantitative weight and atomic percentage of the compositional
with the increasing dopant concentration and this can be attributed elements.
to the increase in the grain size as shown in Fig. 6. Alternative
justification could be the enhancement in crystallinity with the
increasing grain size. However, Bahsi et al. [28] spotted a red shift of 3.5. Photoluminescence (PL) study
the absorption edge of ZnO film after Cu doping and they assumed
that the shift was due to the reduction in the carrier concentra- The room temperature PL spectra of the undoped and dual-
tion contributed by interstitial zinc atoms or oxygen vacancies. This doped nanostructures excited by 325 nm are shown in Fig. 7. The
means that the dopants concentrations also affect the band gap visible or deep trap state emissions (420, 460, 485, 504 and 537 nm)
of the film. A related performance was observed in ZnO/Cu films are by and large stated as the recombination of the electron hole
deposited by magnetron sputtering [29]. pair from the localized states with the energy levels deep seated
2364 J. Arul Mary et al. / Optik 127 (2016) 2360–2365

Pure ZnO valence band and the energy levels of interstitial Zn to Zn vacan-
ZCC 1 cies. A broad PL band in the green region at 537 nm is attributed to
ZCC 2
the defect levels associated with oxygen vacancies or zinc intersti-
ZCC 3
ZCC 4 tial [33,34]. Lin et al. [35] reported that the green emission relates
ZCC 5 to the local level composed by an oxide antisite defect rather than
the oxygen vacancies and interstitial oxygen. On the other hand,
[F(R)hv] 2

it is recognized as the green transition to the singly ionized oxy-

gen vacancy in the ZnO, and this emission results also from the
recombination of the photogenerated hole with the singly ionized
3.17 eV
charge point to such a defect. The intensity of the green emission
3.09 eV 3.11 eV
3.13 eV 3.19 eV 3.22 eV peak extremely decreased with the increased dopant level. This can
be accounted for the increased density of the surface defect states,
3.10 3.15 3.20 3.25 3.30 3.35 because of the increased dopant concentration.
Band gap (eV)

Fig. 5. UV–visible diffuse reflectance spectra of (Zn1−2x Cex Cux ) O (x = 0.00, 0.01, 0.02, 3.6. Antibacterial activity
0.03, 0.04 and 0.05) system.
The antimicrobial activities of the pure and doped samples
were tested against Gram-negative P. aeruginosa, E. coli and Gram-
positive S. aureus, K. pneumonia and B. subtilis bacterial pathogens.
48 3.26 For comparison, the antibacterial activity of the undoped and dual-
46
Crystallite size
Band gap
3.24 doped ZnO at various concentration (25, 50, 75 and 100 ␮l/well)
3.22 were tested by well diffusion method. The zone of inhibition was
44
3.20 estimated from mean diameter around the test sample, measured
Crystallite Size (nm)

in mm. Pure and doped samples at various concentrations except

Band gap (eV)

42 3.18
3.16
(pure ZnO at 25 ␮l) exhibited a clear bactericidal zone of inhibition
40 around each specimen, indicating a noticeable effect against bacte-
3.14
38 ria. The detected mean diameter of inhibition zones for undoped
3.12
ZnO and for dual-doped ZnO values against given bacteria are
36 3.10
shown in Table 2. These results displayed that the dual doped ZnO
3.08 nanostructures have sufficient antibacterial activity for both gram
34
0.00 0.01 0.02 0.03 0.04 0.05 positive (G+) and gram negative (G−) bacteria than undoped ZnO.
Ce,Cu Content
(M)
The dual doped ZnO nanostructures render an effective antibacte-
rial activity than the undoped ZnO. Maximum inhibition zone was
Fig. 6. Variation of the band gap energy of Zn1−2x Cex Cux O (x = 0.00, 0.01, 0.02, 0.03, observed for ZnCC5 followed by ZnCC3 and Pure ZnO. The maxi-
0.04 and 0.05) system. mum zones of inhibition measured were 28 mm against K. moniae
for ZnCC3. The presence of inhibition zone is an indication that
the bacteria have not developed resistance towards the sample,
which has revealed the biocidal activity of ZnO and doped samples.
420
Pure ZnO Sample ZnCC3 showed a maximum zone of inhibition of 4–18 mm
ZCC 1
ZCC 2 against the pathogens. The zone of inhibition at 100 ␮l/well concen-
ZCC 3 tration for ZnCC3 was 16 mm each against E. coli and P. aeruginosa,
ZCC 4 18 mm against Gram-positive S. aureus, 17 mm against K. pneu-
Intensity (a.u)

ZCC 5
460 485
400 450
Wavelength (nm)
Fig. 7. PL spectra of Zn1−2x Cex Cux O (x = 0.00, 0.01, 0.02, 0.03, 0.04 and 0.05) system.
in the band gap, producing lower energy emissions. These diverse
energy levels are generally connected with the structural features,
or surface defects, which may be due to the oxygen vacancies. The
source of the emission at 420 nm is allotted to the electron transi-
tion from the interface trap level at the grain boundary of ZnO to the
valence band [30]. The cause of the blue emission at 460 and 485 nm
is linked to the defect structure of the material [31,32]. This emis-
sion emerges possibly, due to the transitions from zinc interstitial
to zinc vacancies [33]. Hence, the blue emission peak was ascribed
to the electron transition from both the interstitial Zn levels to the
monia, 16 mm and 15 mm against B. subtilis. ZnCC5 showed the
maximum zone of inhibition of 11–28 mm against pathogen. The
zone of inhibition at 100 ␮l/well concentration for ZnCC5 was,
25 mm against E. coli and P. aeruginosa, 27 mm against Gram-
537
positive S. aureus, 25 mm, against K. pneumonia, 28 mm and 22 mm
504
against B. subtilis. Overall, ZnCC5 showed an efficient antibacte-
rial activity against pathogens, due to the enhanced antibacterial
activity. Moreover, nanostructures are believed to be more efficient
500 550
in causing abrasive action on the cell wall and might cause mem-
brane damage. The improved bioactivity of the nanostructures is
attributed to the higher surface area to volume ratio. The nanos-
tructures need more particles to cover a bacterial colony, which
results in the generation of more active oxygen species, and it kills
the bacteria more successfully. The antibacterial activity of nanos-
tructures can may either speedily interact with the microbial cells
causing the interruption of trans membrane electron transfer, dis-
rupting the cell envelope, oxidizing cell components, and producing
secondary products, such as, reactive oxygen species, that can cause
damage. In addition, the destruction of the cell membrane might
directly lead to the leakage of minerals, proteins and genetic mate-
rials causing ultimate cell death [36]. From the antibacterial tests,
we confirmed that the dual-doped ZnO nanostructures render an
effective antibacterial agent, when compared to undoped ZnO.
 J. Arul Mary et al. / Optik 127 (2016) 2360–2365 2365

Table 2
Antibacterial activity of Pure ZnO, ZnCC3, and ZnCC5 samples against pathogens.

Samples Antibacterial activity of given sample zone of inhibition (mm)

Escherichia coli Pseudomonas aeruginosa Staphylococcus aureus Klebsiellap neumoniae Bacillus subtilis

Conc. (␮l/well) 25 50 75 100 25 50 75 100 25 50 75 100 25 50 75 100 25 50 75 100

ZnO – 3 7 9 – 5 7 8 – 7 9 12 – 5 9 12 – 6 9 11
ZnCC3 8 10 12 16 7 12 14 18 6 12 15 17 4 9 12 16 7 11 13 15
ZnCC5 17 21 23 25 18 21 22 27 14 17 22 25 20 23 26 28 11 15 17 22

4. Conclusion
This work demonstrates the simple concept for the synthesis of
undoped and dual-doped ZnO nanostructures with varying doping
levels. The XRD results reveal the wurtzite structure of the samples.
At the same time, the shift in the peak, the change in the values of
cell volume and increase in the crystallite size upon doping were
also observed. SEM characterization results exhibited the hexag-
onal morphology of the nanostructures for undoped sample and
spherical morphology for doped samples with an average size of
about 21 nm. The energy dispersive X-ray spectra confirmed the
presence of Ce and Cu in ZnO system and the weight percentage was
nearly equal to their nominal stoichiometry structure. DRS mea-
surements showed a decrease in the energy gap with increasing
dopants content. The PL results showed that the optical proper-
ties of ZnO nanoparticles were enhanced by doping. The enhanced
bioactivity was demonstrated by studying the antibacterial activ-
ity of the undoped and dual-doped ZnO samples. After doping, the
experimental diameter values of the inhibition zones estimated
were formed to be more. It indicates that the doped ZnO sam-
ples were found to be more effective towards the pathogens, thus
causing greater mechanical damage to the bacteria.
References
[1] V.K. Bajpai, H.R. Kim, C.T. Hou, S.C. Kang, New Biotechnol. 26 (2009) 122–130.
[2] A.M. Szczupak, K. Ulfig, A.W. Morawski, Catal. Today 169 (2011) 249–257.
[3] N.L. Stock, J. Seller, K. Vinodgal, P.V. Kamat, Environ. Sci. Technol. 34 (2000)
950–958.
[4] F. Sayilkana, M. Asilturka, N. Kirazb, E. Burunkayab, E. Arpac, H. Sayilkan, J.
Hazard. Mater. 162 (2009) 1309–1316.
[5] J. Sawai, T. Yoshikawa, J. Appl. Microbiol. 96 (2004) 803–809.
[6] O. Akhavan, E. Ghaderi, Surf. Coat. Technol. 205 (2010) 219–223.
[7] X. Bingshe, N. Meia, W. Liqiao, H. Wensheng, L. Xuguang, J. Photochem. Photo-
biol. A Chem. 188 (2007) 98–105.
[8] C. Karunakarann, R.S. Sakthi, P. Gomathisankar, Mater. Sci. Semicond. Process.
16 (2013) 818–824.
[9] Y.L. Wu, A.I.Y. Tok, F.Y.C. Boey, X.T. Zeng, X.H. Zhang, Appl. Surf. Sci. 253 (2007)
5473–5479.
[10] M. Raffi, S. Mehrwan, T.M. Bhatti, J.I. Akhter, A. Hameed, W. Yawar, M.M.U.
Hasan, Microbiology 60 (2010) 75–80.
[11] P. Madahi, N. Shahtahmasebi, A. Kompany, M. Mashreghi, M.M.B. Mohagheghi,
A. Hosseini, Phys. Scr. 84 (2011) 035801–035805.
[12] Z. Lingling, J. Yunhong, D. Yulong, D. Nikolaos, J. Lars, P. Malcolm, O.A. York,
David, J. Nanopart. Res. 12 (2010) 1625–1636.
[13] P. Amornpitoksuk, S. Suwanboon, S. Sangkanu, A. Sukhoom, N. Muensit, J. Bal-
trusaitis, Powder Technol. 219 (2012) 158–164.
[14] A.J. Huh, Y.J. Kwon, J. Control. Release 156 (2011) 128–145.
[15] G. Maribel, J. Dille, S. Godet, Int. J. Chem. Biol. Eng. 2 (2009) 104–111.
[16] S. Korichi, A. Elias, A. Mefti, A. Bensmaili, Appl. Clay Sci. 59 (2012) 76–80.
[17] D.V. Stass, J.R. Woodward, C.R. Timmel, P.J. Hore, K.A. McLauchlan, Chem. Phys.
Lett. 329 (2000) 15–22.
[18] L. Perreux, A. Loupy, Tetrahedron 57 (2001) 9199–9223.
[19] M. Rezaei, A.H. Yangjeh, Appl. Surf. Sci. 265 (2013) 591–596.
[20] R.S. Zeferino, M.B. Flores, U. Pal, J. Appl. Phys. 109 (2011) 014308.
[21] D. Gao, J. Zhang, G. Yang, J. Zhang, Z. Shi, J. Qi, Z. Zhang, D. Xue, J. Phys. Chem. C
114 (2010) 13477–13481.
[22] C.X. Xu, X.W. Sun, X.H. Zhang, L. Ke, S.J. Chua, Nanotechnology 15 (2004)
856–861.
[23] K.J. Chen, T.H. Fang, F.Y. Hung, L.W. Ji, S.J. Chang, S.J. Young, Y.J. Hsiao, Appl.
Surf. Sci. 254 (2008) 5791–5795.
[24] H. Mohseni, H. Shokrollahi, I. Sharifi, K. Gheisari, J. Magn. Magn. Mater. 324
(2012) 3741–3747.
[25] G. Srinivasan, R.T.R. Kumar, J. Kumar, Sci. Technol. 43 (2007) 171–177.
[26] J. Yang, J. Wang, X. Li, J. Lang, F. Liu, L. Yang, H. Zhai, M. Gao, X. Zhao, J. Alloys
Compd. 528 (2012) 28–33.
[27] B. Hapke, Theory of Reflectance and Emittance Spectroscopy, University Press,
Cambridge, 1993.
[28] Z.B. Bahsi, A.Y. Oral, Optic. Mater. 29 (2007) 672–678.
[29] X.T. Hao, J. Ma, D.H. Zhang, T.L. Yang, H.L. Ma, Y.G. Yang, C.F. Cheng, J. Huang,
Appl. Surf. Sci. 183 (2001) 137–142.
[30] R. Wu, Y. Yang, S. Cong, Z. Wu, C. Xie, H. Usui, K. Kawaguchi, N. Koshizaki, Chem.
Phys. Lett. 406 (2005) 457–461.
[31] S. Muthukumaran, R. Gopalakrishnan, J. Mater. Sci. Mater. Electron. 23 (2012)
1393–1401.
[32] U.N. Maiti, P.K. Ghosh, S. Nandy, K.K. Chattopadhyay, Phys. B 387 (2007)
103–108.
[33] J. Ding, X. Yana, Q. Xue, Mater. Chem. Phys. 133 (2012) 405–409.
[34] Y. Wu, W. Wu, X.M. Zou, L. Xu, J.C. Li, Mater. Lett. 86 (2012) 182–185.
[35] B.X. Lin, Z.X. Fu, Y.B. Jia, Appl. Phys. Lett. 79 (2001) 943–945.
[36] R.K. Dutta, B.P. Nenavathu, M.K. Gangishetty, A.V.R. Reddy, Colloids Surf. Bioin-
terfaces 94 (2012) 143–150.