Superlattices and Microstructures 81 (2015) 215225

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Superlattices and Microstructures

journal homepage: www.elsevier.com/locate/superlattices

Surfactant mediated synthesis of ZnO

nanospheres at elevated temperature, and their
dielectric properties
Damian C. Onwudiwe a,, Tanvir Arn b, Christien A. Strydom a
a
Chemical Resource Beneciation (CRB) Research Focus Area, North-West University, Private Bag X6001, Potchefstroom 2520,
South Africa
b
Environmental Materials Division, CSIR-National Environmental Engineering Research Institute (CSIR-NEERI), Nehru Marg, Nagpur
440020, India

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

Article history: ZnO colloidal spheres were prepared using a simple surfactant
Received 19 November 2014 mediated approach via a two-stage reaction process, involving
Received in revised form 5 February 2015 the synthesis of nanoparticles and the assembly of the nanoparti-
Accepted 6 February 2015
cles to obtain nanospheres. The present work pointed out a simple
Available online 14 February 2015
and green way of converting ZnO nanoparticles into ZnO nano-
spheres. The structural properties and the crystalline phase of the
Keywords:
ZnO
synthesized nanospheres were characterized by transmission elec-
Nanoparticles tron microscopy (TEM), scanning electronic microscopy (SEM), and
Nanospheres powder X-ray diffraction (XRD). The morphology of the colloidal
Dielectric properties ZnO nanosphere observed at high resolution showed a nanocrys-
Structural properties talline substructure, and XRD indicated the hexagonal phase of
zinc oxide with a high purity. The dielectric properties were stud-
ied over a frequency range of 1 Hz1 MHz at room temperature,
and in the framework of complex dielectric permittivity and com-
plex electric modulus formalisms. The evolution of the complex
dielectric permittivity as a function of frequency at room tem-
perature was investigated.
2015 Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +27 18 299 1068; fax: +27 18 299 2350.
E-mail address: dcconwudiwe@gmail.com (D.C. Onwudiwe).

http://dx.doi.org/10.1016/j.spmi.2015.02.003
0749-6036/ 2015 Elsevier Ltd. All rights reserved.
216 D.C. Onwudiwe et al. / Superlattices and Microstructures 81 (2015) 215225

1. Introduction

Nanospheres are made up of several closely packed and randomly aligned nanocrystallites.
Monodispersed nanospheres and spherical structures have become a new study focus because of their
potential applications in optics, electrics, catalysis, and sensing devices. The preparation of new
monodispersed nanospheres and their functional transformation has generated a lot of research inter-
est [1]. Zinc oxide (ZnO) is one of the most exploited n-type semiconducting metal oxide materials
because of its tunable structural, morphological, optical, electrical and sensing properties [2]. The
non-toxic nature also made ZnO available for wide range of applications such as ultraviolet light emit-
ters, lasers, piezoelectric material, window materials for solar cells, and thin lm transistors [3,4].
One of the fascinating interests of ZnO lies in its structure-dependent properties. Therefore,
research focused on the design and syntheses of ZnO nanomaterials with different structures are
important. The synthesis of ZnO nanospheres using different routes has been reported. Tong et al.
[5] reported the preparation of zinc oxide nanospheres by a solution plasma process (SPP), in which
plasma is introduced in an aqueous environment containing chemical agents. ZnO hollow nano-
spheres synthesized using polymeric micelles with coreshellcorona structures, as soft-templates,
have been reported [6]. The polymer, which possesses some anionic shell block, was believed to facil-
itate the formation of hollow nanospheres through electrostatic interaction of the Zn2+ ions with the
ACOO ions of the polymer, followed by a precipitation/deposition reaction under mild alkaline con-
ditions. Qian et al. [7] reported the preparation of uniform ZnO nanospheres consisting of a shell of
closely packed nanoparticles with a shell wall thickness of a few tens of nanometers by controlled pre-
cipitation of metal cations with urea in the presence of carbonaceous saccharide nanospheres as hard
templates. A facile hydrothermal method assisted with different surfactants including polyethylene
glycol (PEG), polyvinylpyrrolidone (PVP), glycine, and ethylene glycol (EG) has been devised to prepare
ZnO nanospheres amidst other low dimensional nanostructures [8]. Monodispersed ZnO colloidal
spheres with diameters in the range of 300 nm to 1 lm, have been synthesised from a solution of zinc
acetate and polyethylene glycol (PEG) at 135 C [9]. The synthesis of uorescent porous zinc sulphide
nanospheres by a facile gum arabic-assisted hydrothermal procedure has been reported [10].
ZnO is a wide band-gap semiconductor (Eg = 3.3 eV), and its electrical conductivity is mainly due to
zinc excess at the interstitial position [11]. A large volume percentage of crystalline material consists
of grain or interface boundaries. These boundaries contain defects such as dangling bonds and vacan-
cies, which can cause a positive or negative space charge distribution at interfaces. Studies on the con-
ductivity of nanomaterials are important for gaining a better knowledge on the ionic conduction
mechanism. Dielectric behaviour can effectively be used to study the electrical and electrochemical
properties of the grain boundaries, and also shows the effects of temperature and frequency on con-
duction in the nanostructured material [12]. The dielectric parameters, such as the dielectric constant
(er) and dielectric loss (tan d) are the basic electrical properties of the ZnO nanoparticles.
In this paper, we report the preparation of ZnO nanospheres using a two-step approach, which
involves the preparation of the nanoparticles, followed by a facilitated alignment of the nanoparticles
to form nanospheres. The structural properties and the dielectric behaviour of the materials were
determined and are discussed.

2. Materials and methods

Zinc acetate, polyvinylpyrrolidone (average mol wt 40,000), sodium hydroxide, and hydrogen per-
oxide were purchased from Merck, SA. The reagents were of analytical grade and were used as
received. High grade Olive oil was obtained from a local supermarket (Dischem, SA).

2.1. Preparation of ZnO nanospheres

(i) 4.0 g zinc acetate and 2.5 g polyvinylpyrolidone (PVP) was dissolved in 50 mL water. The solu-
tion was stirred for 15 min at room temperature, and then sonicated for 2 h. The water was
removed by slow evaporation, and the resulting white solid product was grinded in a mortar.
 D.C. Onwudiwe et al. / Superlattices and Microstructures 81 (2015) 215225 217

ZnO nanorods were then prepared by thermal decomposition of the obtained solid at 330 C for
6 h in a tube furnace (Elite Thermal System) under nitrogen ow (75 mL/min). After the pyro-
lysis process, the resultant white solid powder was washed with de-ionised (DI) water and
ethanol to remove any ions from the nal products, and nally dried at 60 C in air. During
the process, the PVP polymeric network slowly burns off from the outer surface of the complex
before 200 C, and decomposition of the zinc acetate at 330 C results into rod shaped ZnO
nanoparticles. This sample is denoted as rZnO.
(ii) 50 mL Zn(NO3)26H2O aqueous solution (0.05 mol L1) and 50 mL NaOH aqueous solution
(0.05 mol L1) were reacted, and the resultant zinc hydroxide (Zn(OH)2) precipitate was cen-
trifuged. The precipitate was separated, and re-dispersed in distilled water. The solution was
again centrifuged, and the precipitate was then dispersed in 50 mL H2O2 aqueous solution
(1 mol L1). The dispersed solution was heated at 75 C for 2 h to yield a translucent sol of zinc
peroxide which was dried at 75 C for 12 h. The obtained powder was heated at 300 C for 2 h in
air to obtain spherical shaped ZnO nanoparticles [13], which are denoted as sZnO.

In the second phase of the reaction, 0.05 g of the nanoparticles was dissolved in 15 mL N,N-
dimethyformamide (DMF), followed by the addition of 10 mL olive oil and stirred for 60 min. The mix-
ture was heated and the temperature maintained at 120125 C for 30 min. The mixture was then
cooled to room temperature, ethanol was added and the mixture was centrifuged. The product was
separated and washed several times with water. The samples obtained from rZnO and sZnO were rep-
resented as ZO1 and ZO2, respectively.

2.2. Characterization techniques

The structural characteristics of the nanoparticles were examined using a Rntgen PW3040/60
XPert Pro X-ray diffractometer with Ni-ltered Cu Ka radiation (k = 1.5405 A) at room temperature,
in the 2h range of 3060 with scanning rate of 1 deg/min. XPert HighScore Plus PW3212 software
was used for the analysis, and the phase identication was carried out using the standard JCPDS.
The surface morphology of the lms was examined using a Quanta FEG 250 Environmental Scanning
electron microscope (ESEM). Transmission electron microscopic (TEM) and high resolution transmis-
sion electron microscopic (HRTEM) images were collected using a TECNAI G2 (ACI) instrument oper-
ated at an accelerating voltage of 200 kV. Electrical properties were measured by means of AC
impedance spectroscopy using the two-probe method on a Solartron 1260 impedance analyser in
the frequency range of 5 Hz6.5 MHz, and operated with an AC signal of 50 mV.

3. Results and discussions

3.1. Preparation of nanospheres

The preparation of the nanospheres was carried out in a two-stage reaction process, involving the
synthesis of nanoparticles, and subsequent aggregation of the nanoparticles in olive oil to form nano-
spheres. Olive oil has recently been exploited as capping agent to synthesize nanocrystals [1416] as a
new route towards the use of more environmentally friendly solvents in nanoparticles synthesis. The
olive oil is in liquid state at room temperature with a boiling point above 340 C, rendering it easy to
use. Olive oil is predominantly a triacylglyceride of long chain fatty acids with free fatty acids (FFA)
including oleic, linoleic and linolenic acids; other minor components are monoterpenes and long chain
phenolic esters [1721]. Oleic acid ((C17H35COOH) or CH3A(CH2)7ACH@CHA(CH2)7ACOOH) is
monosaturated and makes up 85% of olive oil [22]. In the current process, olive oil was found to play
an important role in the production of ZnO nanospheres. When olive oil was introduced into the solu-
tion containing ZnO, and stirred at room temperature, the nanospheres were not visible. It is possible
that the oleic acid initially coordinated with the ZnO nanoparticles to form a complex. Then, as the
temperature increases, small nanoparticles were assembled into large secondary particles, which were
nally assembled into the nanospheres. The presence of the nanospheres at elevated temperature
indicates the role of heat during the aggregation process.
218 D.C. Onwudiwe et al. / Superlattices and Microstructures 81 (2015) 215225

3.2. Morphologies and structural properties

A typical SEM image of ZnO prepared by the thermal decomposition of zinc acetate-PVP at 330 C,
and zinc peroxide at 300 C, are respectively presented in Fig. 1(a) and (b). The SEM images reveal that
ZnO synthesized using these techniques consist of aggregates of rods (Fig. 1(a)) and spheres (Fig. 1(b))
with nearly uniform sizes. The transmission electron micrographs in Fig. 1(c) and (d), conrms that
the particles are rods and spheres.
Representative TEM images of ZO1 and ZO2 are shown in Figs. 2 and 3. The low magnication
images in Figs. 2(a) and 3(a) reveal that the synthesized particles consist of nanospheres, whose sizes
are approximately 100200 nm and 30150 nm in diameter, respectively. rZnO nanoparticles form
bigger sized nanospheres of closer size range than the spherical particles from sZnO. Hence, indicating
that the shape of the precursor particles plays a role in the assembly process. HRTEM images recorded
for ZO1 and ZO2 are shown in Figs. 2(b) and 3(b). The images reveal that the synthesized nanospheres
consist of aggregate of individual nanoparticles. The presence of lattice fringes (insets, Figs. 2(c) and
3(c)) indicates the crystallinity of the particles. The measured lattice spacing of the crystallographic
plane is 0.25 nm, which corresponds with the (0 0 2) plane of hexagonal ZnO [23]. It is expected that
good crystallinity associated with nanostructured materials would enhance the electrical properties
by increasing the mobility of charge carriers, as well as minimizing the defects [24,25].

(a) (b)

(c) (d)

200 nm

Fig. 1. SEM images of (a) rZnO, (b) sZnO; and TEM images of (c) rZnO, (d) sZnO after pyrolysis of zinc acetate-PVP at 330 C, and
zinc peroxide at 300 C.
 D.C. Onwudiwe et al. / Superlattices and Microstructures 81 (2015) 215225 219

(a) (b) (c)

0.25 nm

2 nm

Fig. 2. TEM images of (a) ZO1, (b) single ZnO nanosphere showing the nanocrystalline substructure of the material, and inset (c)
single nanoparticle showing the lattice fringes.

(a) (b) (c)

0.25 nm

2 nm

5 nm

Fig. 3. TEM images of (a) ZO2, (b) single ZnO nanosphere showing the nanocrystalline substructure of the material, and the
inset (c) single nanoparticle showing the lattice fringes.

Temperature usually plays an important role in the assembly of periodic structures. Under the
inuence of temperature and the solvent, the precursor ZnO nanoparticles prefer to aggregate into
spherical nanospheres. The formation process of the nanospheres can be identied by Fig. 4(a) and
(b), which were obtained from the products collected after stirring at room temperature for 2 h
(Fig. 4(a)), and at 120125 C for 20 min (Fig. 4(b)). Fig. 4(a) shows the presence of aggregates with
no denite alignment, while at elevated temperature the alignment into nanospheres with denite
morphology gradually occurs, as evident in Fig. 4(b). The organic molecule can be absorbed on the sur-
face of the nanosized particles, thus acting as structure directing agents and inuencing the aggrega-
tion and assembly processes of the nanoparticles.
Fig. 5 shows the XRD patterns of rZnO, sZnO and ZO1. All the samples show peaks at scattering
angles (2h) around 31.8, 34.5, 36.3, 47.4, 56.4, 62.8, 67.8, and 68.9 which correspond to the
220 D.C. Onwudiwe et al. / Superlattices and Microstructures 81 (2015) 215225

(a) (b)

Fig. 4. TEM images of ZnO nanoparticles in DMF-olive oil solution after stirring (a) at room temperature for 1 h and (b) at 120
125 C for 20 min.

reections from the 1 0 0, 0 0 2, 1 0 1, 1 0 2, 1 1 0, 1 0 3, 1 1 2, and 2 0 1 crystal planes of the hexagonal

phase of zinc oxide [26,27]. The diffraction peaks have lattice constants of a = 0.325 nm and
c = 0.521 nm from JCPDS card no. 04-007-9627. No other peaks (impurity) are apparent, indicating
the purity of the samples [28]. The broad peak indicates the nanocrystalline nature of the particles
[29]. Similar diffraction peaks was observed after the second phase surfactant mediated synthesis
of nanospheres (Fig. 5(c)). Thus, the change in morphology of the nanoparticles does not alter the crys-
talline phases of the samples.

3.3. Dielectric properties

The electrical parameters in the ZnO nanosphere are comprised of, (i) the impedance which is
denoted as Z, (ii) the real part of the dielectric permittivity which is denoted as e0 , and (iii) the ima-
ginary part of dielectric permittivity or dielectric loss denoted as e00 . The ac conductivity, rac , was mea-
sured, the dielectric constant, e0 , and dielectric loss, e00 , of the samples were calculated by using the
following relationships [30]:
ct
e0 1
e0 A
101
100
002

60000
110

103

112
102

201

202
200

004

50000 (c)
Intensity (a.u)

40000

30000
(b)
20000

10000

0 (a)

40 60 80
2 theta (degrees)

Fig. 5. XRD patterns for the (a) rZnO, (b) sZnO, and (c) ZO1.
 D.C. Onwudiwe et al. / Superlattices and Microstructures 81 (2015) 215225 221

rac
e00 2
e0 x
where t is the thickness of the pellet, A is the area of cross section of the sample, e0 is the permittivity
of the free space and rac is the ac conductivity of the sample.
The ac conductivity of each sample is calculated using conductance (G) as follows:
tG
rac 3
A
The values of e0 and e00 were used to determine the loss tangent tan d, using the expression [30]:
e00 e0 tan d 4

where d is the phase angle between the electric eld and the polarization of the dielectric constant.
The estimated values of e0 and e00 were used to calculate the real part M 0 and imaginary part M 00
of the electric modulus as follows [30]:
e0
M0 5
e02 e002

e00
M00 6
e e002
02

The real part of the dielectric permittivity or the dielectric constant (e0 ) and the imaginary part of
dielectric permittivity or the dielectric loss (e00 ) for both ZO1 and ZO2 measured in the frequency range
of 1 Hz1 MHz, at room temperature. The measurement curves are shown in Figs. 6 and 7 respectively
for ZO1 and ZO2. The dielectric constant, e0 , is observed to decrease rapidly at lower frequencies and
also shows a frequency independent behaviour in the higher frequency region [31]. Migration of ions
at higher temperatures causes e0 x to increase. In nanocrystalline materials, most of the atoms reside
in grain boundaries, which become electrically active as a result of charge trapping. The dipole
moment easily follows the changes in electric eld, especially at low frequencies. Hence the contribu-
tions to the dielectric constant increase through space charge polarization and rotation polarization,
which occurs mainly in interfaces. This is the reason the dielectric constant of nanostructured mate-
rials is expected to be larger than that of bulk material [32].

Fig. 6. Variation of the real part of dielectric constant with respect to frequency at room temperature for (a) ZO1 and (b) ZO2.
222 D.C. Onwudiwe et al. / Superlattices and Microstructures 81 (2015) 215225

Fig. 7. Variation of the imaginary part of dielectric constant with respect to frequency at room temperature for (a) ZO1 and (b)
ZO2.

Fig. 8. Variation of the real part of the modulus with respect to frequency at room temperature for (a) ZO1 and (b) ZO2.

In the higher frequency region, the rotation of the charge carriers is hampered. Their oscillations
begin to align behind the applied eld thereby resulting in the reduction of the dielectric permittivity,
e0 x. The relaxation phenomena in dielectric materials are found to be associated with frequency
dependent orientational polarization. In the low frequency region, the permanent dipoles align them-
selves along the respective elds and contribute to the polarization of the dielectric permittivity. The
variation in the eld too is rapid in the higher frequency region for the dipoles to align themselves,
thus the contribution to the polarization as well as to the dielectric permittivity becomes negligible.
Therefore, the dielectric permittivity, e0 x, decreases with an increase in the frequency. In polycrys-
talline material, while the grains display semi-conducting behaviour, the grain boundary acts as an
 D.C. Onwudiwe et al. / Superlattices and Microstructures 81 (2015) 215225 223

Fig. 9. Variation of the imaginary part of modulus with respect to frequency at room temperature for (a) ZO1 and (b) ZO2.

insulator [31]. One of the reasons for the decrease in the dielectric permittivity in both ZO1 and ZO2 as
frequency increased, is the increase in space charge polarization due to the structure of their grain
boundary interfaces. On the other hand, the values of both e0 and e00 are found to be high in the lower
frequency region and then rapidly decreased with the increase in frequency for both the samples.
The electrical relaxation of ZO1 and ZO2 was analysed using the electric modulus approach. The
electric modulus, M , is dened in terms of the reciprocal of the complex dielectric constant, e  x:

1
M 7
e  x

M 0 x M 00 x 8
0 00
where M is the real part of the complex modulus and M is the imaginary part of the complex mod-
ulus. Both parameters are calculated by using Eqs. (5) and (6). The frequency dependence of M 0 x and
M00 x of both ZO1 and ZO2, at room temperature, are shown in the Figs. 8 and 9 respectively.
Figs. 8 and 9 describe the relaxation nature of the dielectric properties of both materials. M 0 x and
M00 x increase with an increase in the frequency region investigated [33]. The frequency above the
peak maximum, M 00 x, can be determined in the range for which charge carriers are found to be
mobile at long distances. At sufciently high temperature the relaxation of both ZO1 and ZO2 is
dominated by the sharp increase of the dielectric constant at low frequencies and at lower tem-
peratures. The space charge and ion jump polarization are functions of temperature. So when tem-
perature increases, both the space charge and ion jump polarization decreases, resulting in a
decrease in the dielectric constant. At frequencies above the peak maximum, M 00 x, the carriers
are partially restricted to potential wells, which are mobile at short distances, making it the only local-
ized motion within the wells. The relaxation time, s, is also calculated from the M 00 x peak by using
the relation, s 1=xpeak . The ZnO nanospheres would act as good nanocrystalline materials in dielec-
tric devices.

4. Conclusions

Nanoparticles of ZnO, with rod and spherical morphologies, were synthesized via the thermal
decomposition of their precursor complexes. Olive oil was used as a structure directing agent in the
presence of DMF, to inuence the aggregation and the assembly process of the nanoparticles into
nanospheres. The crystal structure and morphology of the particles were determined using XRD
and TEM studies. The dielectric characteristics of the ZnO nanospheres were measured in the frequen-
cy range of 1 Hz1 MHz, at room temperature. The dielectric studies revealed that both the dielectric
224 D.C. Onwudiwe et al. / Superlattices and Microstructures 81 (2015) 215225

constant and dielectric loss decrease with an increase in frequency. The variation of the electric mod-
ulus, M 00 , as a function of frequency shows the drastic shifting of the peaks towards the higher frequen-
cy region, which suggests that there is a distribution in ionic relaxation time.

Acknowledgements

The authors acknowledge the nancial support of North-West University and the Chemical
Research Beneciation (CRB) Research Focus Area. The work presented in this paper is based on the
research supported by the National Research Foundation of South Africa. Any opinion, nding or con-
clusion or recommendation expressed in this material is that of the author(s) and the NRF does not
accept any liability in this regard.

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