Materials Letters 161 (2015) 124–127

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Materials Letters
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Green synthesis of ZnO nanoparticles via Agathosma betulina natural

extract
F.T. Thema a,b, E. Manikandan a,b, M.S. Dhlamini a, M. Maaza a,b,n
a
UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392,
Pretoria, South Africa
b
Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure road, Somerset West 7129, PO Box 722, Somerset
West, Western Cape, South Africa

art ic l e i nf o a b s t r a c t

Article history: This contribution reports on the synthesis and the main physical properties of ZnO nanoparticles syn-
Received 20 July 2015 thesized for the first time by a completely green process using Agathosma betulina plant extract as an
Received in revised form effective chelating agent. The surface/interface and volume room temperature properties of these quasi-
9 August 2015
spherical 15.8 nm in size ZnO nanoparticle by transmission electron microscopy, energy dispersive X-Ray
Accepted 10 August 2015
Available online 10 August 2015
Spectroscopy, X-rays diffraction, attenuated total reflection IR and Raman spectroscopy are reported.
Likewise, a spark sintered pellet made of such nanoparticles exhibited a significant nonlinear current–
Keywords: voltage exponential response characteristic of a varistor.
Green synthesis & 2015 Elsevier B.V. All rights reserved.
Zinc oxide
Nanoparticles
Agathosma betulina’s extract

1. Introduction unbalance and generated hazardous waste by the two major

Zinc oxide (ZnO) is one of the most exploited n-type semi-
conducting metal oxide materials due of its tunable & multi-
functional morphological, photonic and spintronic properties [1–
4]. It is characterized by a wide direct band gap of 3.37 eV and a
high excitation energy of 60 meV. Owing to these characteristics,
ZnO is used widely in many devices, including surface acoustic
wave devices, gas sensing and optoelectronics [5–6]. This multi-
functionality of ZnO has been demonstrated successfully via sev-
eral pioneering devices among which one could mention minia-
turized semiconductor lasers, optically transparent electrodes, ul-
traviolet photodetectors, transparent thin-film transistors and
metal–insulator–semiconductor diodes [3–7].
The synthesis of nanoscaled ZnO is dominated by physical and
chemical processes. The physical methodologies include thermal
evaporation, chemical vapor deposition, pulsed laser deposition,
metal–organic chemical vapor deposition and molecular beam
epitaxy among others [8–12]. Generally, such processes require
high vacuum and are energy consuming. While the chemical
methods such as solvothermal, sol–gel, sonochemical, spray pyr-
olysis, hydrothermal, and electrodeposition processes [13–17] are
cost effective and mass-production oriented, they are en-
vironmentally unfriendly. To mitigate the problem of energy
n
Corresponding author.
E-mail address: Maaza@tlabs.ac.za (M. Maaza).
processes, greener approaches are being researched. One such a
promising method is the biosynthesis of nanoparticles using
plant-based extracts. Indeed, this biosynthesis approach has been
demonstrated to be effective in the synthesis of metal and oxide
nanoparticles [18–20]. While significant work has been reported
on the use of several plant-based extracts to prepare various metal
nanoparticles not much is reported on the use of these extracts for
bio-synthesis of oxides in general and ZnO nanoparticles
specifically.
Complementing the limited literature on biosynthesized ZnO
using natural extracts [20–23], this contribution reports for the
first time the green synthesis of highly crystalline single phase
zincite ZnO nanoparticles by using Agathosma betulina natural
extract as an effective chelating agent. The physical characteristics
of such ZnO nanoparticles are investigated by a diverse techniques
to confirm their single zincite phase.
2. Synthesis: green process via Agathosma betulina natural
extract
A. betulina is a plant commonly known as Buchu [24]. The
chemical composition of its extract is reported in reference [18].
15 g of A. betulina dry leaves were weighed and washed with
distilled water (dH2O) at room temperature. The leaves were then
immersed in dH2O to extract the green dye at
100 °C for 1 h. The

http://dx.doi.org/10.1016/j.matlet.2015.08.052
0167-577X/& 2015 Elsevier B.V. All rights reserved.
 F.T. Thema et al. / Materials Letters 161 (2015) 124–127
dye extract solution (pH 5) was filtered twice to eliminate residual
solids. Analytical grade hydrated zinc nitrate Zn(NO3)2  6H2O was
considered as a zinc precursor. 6.0 g of zinc nitrate was homo-
geneously mixed with 100 ml of A. betulina solution and heated at
100 °C for 2 h. Following such a phase, a precipitate was observed.
This precipitate was washed with dH2O repeatedly and centrifuged
at 1000 rps for 10 min and subsequently dried in an oven at
100 °C. The dried precipitate was annealed in an open furnace at
various temperatures within the range 100–500 °C for 2 h. The
annealing at 500 °C was the optimized condition to obtain highly
crystalline ZnO nanoparticles.
3. Results & discussion
3.1. Morphology & microscopy observations
Fig. 1 reports a typical a High Resolution Transmission Electron
Microscopy (HRTEM) image of the optimized sample (Annealed at
500 °C). It consists of quasi-spherical agglomerated nano-scaled
particles. The digitization phase of various images indicates that
the nanoparticles' diameter Ø ranges from 12 to 26 nm. By fitting
the histogram data with a Gaussian distribution, 〈Ø〉 was found to
be 15.8 70.2 nm (Fig. 1b). The Selected Area Electron Diffraction
(SAED) profile of Fig. 1c indicates via its combined spotty ring
patterns the highly crystallized structure of the synthesized na-
noparticles. Fig. 1d reports an HRTEM image of single nano-
particles revealing a series of distinguishable reticular plans with
reticular distances dhkl of 0.25 nm and 0.28 nm. These values fit
with the (101) and (100) reticular distances of the ZnO hexagonal
wurtzite structure (JCP 00-036-1451).
3.2. Elemental & structural analysis
Fig. 2a reports a typical Energy Dispersive X-Ray Spectroscopy
(EDS) spectrum. The spectrum of the optimized sample confirmed
the presence of zinc and oxygen in the powder. The appearance of
C (0.26 keV) and Cu (8.09 keV) are attributed to the C coated Cu
grid support. Consequentially, there are no other elements except
Zn and O sustaining the pure chemical form of the formed ZnOy
Fig. 1. TEM image of the optimized ZnO particles (a) with their size distribution (b), their SAED pattern (c) and HRTEM image (d).
125
nanoparticles. Fig. 2b reports a typical X-Rays Diffraction (XRD)
profile of the optimized nanoparticles (λCukα1 ¼1.5406 Å). The
8 observed Bragg peaks match entirely with the single phase ZnO
wurtzite pattern (JCP 00-036-1451). The deduced lattice constants
are 〈aexp.〉 ¼3.24 and 〈cexp.〉 ¼5.93 Å. Relatively to bulk ZnO, there is
a significant difference in the clattice value indicating that the [001]
direction is under elongation conditions. Likewise, the ratio Δd/
dbulk (Δd ¼[dexp  dbulk]) is negative except for the [002] reticular
direction sustaining the fact that the c-direction is under stretch-
ing conditions. The Debye-Scherrer approximation 〈Ø〉∼0.9λ/ ΔΘ1/
2 cos(ΘB) gives an average size of the optimized ZnO nanoparticles
of ∼19.4 nm in line with the TEM results.
3.3. Vibrational properties
To validate again the zincite nature of the synthesized nano-
particles and their purity, Attenuated Total Reflection-Fourier
Transform Infrared spectroscopy (ATR-FTIR) studies were per-
formed. Fig. 3a reports the typical ATR-FTIR spectrum of the
pressed powder in the spectral range of 400–4000 cm  1). The IR
transmission is plotted so to single out the major absorptions
observed at lower wavenumbers. One can distinguish a broad
band observed at 3437.5 cm  1 attributed to the O–H stretching
mode of hydroxyl group. The characteristic bands corresponding
to the Zn–O stretching mode are observed at 493.8 and
846.2 cm  1[25]. In view of the relative intensity of the Zn–O
modes to the adsorbed OH compounds, one can pre-conclude on
the high crystallinity and purity of the synthesized ZnO nano-
particles. Like most wurtzite crystal structure materials, ZnO be-
longs to the hexagonal system with C6v4(P63mc) with two formula
units per primitive cell where all atoms occupy C3v sites. Ac-
cording to the group theory, ZnO has active photon modes of A1, E1
and 2 E2 type and inactive photon B1[26]. Fig. 3b displays the
Raman spectrum using the 473 nm excitation laser line with an
average excitation power of 2.48 mW in the spectral range of 200–
1000 cm  1. It consists of a dominant peak centered at 439.6 cm  1
attributed to E2(high) mode of wurtzite ZnO [27]. The band at
505 cm  1 maybe associated with oxygen deficiency or oxygen
vacancies in ZnO [28]. The mode at 332.8 cm  1 is generally asso-
ciated to the second order structure of 2E2(M). The disorder–
126 F.T. Thema et al. / Materials Letters 161 (2015) 124–127

Fig. 3. (a) ATR-FTIR spectrum of the optimized ZnO nanoparticles and (b) their
Raman spectrum.

Fig. 2. (a) EDS spectrum of the optimized ZnO nanoparticles and (b) their XRD
pattern.

related small peaks were also observed at around 575 cm  1 which

are usually assigned to the A1 longitudinal optical, A1(LO) mode
[26]. This mode is normally assigned to lattice disorders origi-
nating from foreign atoms or intrinsic defects [29–31].

3.4. Varistor response

In view of the nanoscale aspect of the synthesized ZnO nano-

particles and the corresponding large grain boundaries, they
should exhibit a significant nonlinear current–voltage (I–V) char-
acteristics and hence could be used in the varistor technology for
the protection of electric equipment from degradations caused by
overvoltage peaks and electrostatic discharges such as those re-
lated to lightning events in aeronautical applications. In view of
testing the varistor properties of the synthesized ZnO nano-
particles, a spark sintered pellet was fabricated to avoid a growth Fig. 4. Varistor response of a spark sintered pellet made of the optimized ZnO
of the ZnO nanoparticles’ size during the sintering. Fig. 4 displays nanoparticles.
the variation of the current density “J” versus the electric field “E”.
The nonlinearity variation profile J ¼f(E) is equivalent to a non- electrical resistance which decreases as the voltage is raised and
ohmic current–voltage characteristic that is similar to that of a low resistance at high voltages. The corresponding fitting curve is
diode. In contrast to a diode however, it has the same character- J¼ 1.19  10  19 exp(0.1065 E)þ0.089 with χ2 of 0.9998. The elec-
istic for both current's directions. At low voltage it has a high tric field at 0.1 and 1 mA/mm2 is 344.9 and 408.1 V/mm
 F.T. Thema et al. / Materials Letters 161 (2015) 124–127 127

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