Journal of Alloys and Compounds 646 (2015) 425e430

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Green synthesis of ZnO nanoparticles by Aspalathus linearis: Structural

& optical properties
A. Diallo a, b, B.D. Ngom a, b, E. Park a, b, c, M. Maaza a, b, *
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
c
Nelson Mandela African Institute for Science & Technology, Arusha, Tanzania

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

Article history: This contribution reports for the 1st time on the synthesis and the main physical properties of ZnO
Received 2 May 2015 nanoparticles synthesized by an entirely green physical-chemistral process using Aspalathus linearis's
Received in revised form natural extract as an efficient reduction/oxidizing agent. Their structural and optical properties by
19 May 2015
electron microscopy, X-rays diffraction, Raman and X-rays photoemission spectroscopies as well as room
Accepted 21 May 2015
Available online 20 June 2015
temperature photoluminescence are reported.
© 2015 Elsevier B.V. All rights reserved.
Keywords:
Green synthesis
Zinc oxide
Nanoparticles
Aspalathus linearis extract

1. Introduction well as for optically transparent transistors [1e4]. Likewise, the

ZnO, also known as Zincite, is a wide and direct band-gap
semiconductor “~3.7 eV” at room temperature. It has similar
wurtzite crystal structure and optical properties as those of GaN
and hence has attracted a significant interest worldwide above its
initial potentiality as the ideal candidate for blue light emitting
diodes applications. Relatively to GaN, ZnO being sufficiently stable
with a melting temperature of 2248 K, can withstand high tem-
perature treatments associated with doping and forming ohmic
contacts. The intrinsic properties of ZnO make it an excellent
candidate as the material of choice for short wavelength opto-
electronic and photonic devices. Most notable among these prop-
erties is the high excitonic binding energy of 60 meV which allows
for high efficiency operation of devices at and above room tem-
perature. Moreover, announcements about p-type ZnO have been
made; hence this material could be potentially important for
tunnel-junction interconnects in tandem-junction solar cells as
* Corresponding author. 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.
E-mail addresses: Maaza@tlabs.ac.za, Maazam@unisa.ac.za (M. Maaza).
well established multi-functionality of doped ZnO as a transparent
conducting oxide of choice, an effective piezoelectric, a selective
gas sensor and an efficient catalyst support among others, has
made it as one of the most studied simple oxide in its nano-scaled
form in the modern era [5].
ZnO has been synthesized in a plethora of shapes with a nano-
size controlled manner in view of targeted applications in elec-
tronic, photonic and spintronic devices. A rich variety of physical
(vapor-phase process) and chemical (solution phase) methodolo-
gies were used to synthesize undoped or doped ZnO [6]. The vapor-
phase process includes molecular beam epitaxy [7], metal-organic
chemical vapor deposition [8], sputtering method [9], pulsed laser
deposition [10], infrared irradiation [11], thermal decomposition
[12],and thermal evaporation and condensation [13] which are
favored for the high quality of the ZnO final product. However these
methods necessitate high vacuum and high temperatures. In
opposite to the physical based processes, the solution phase routes,
based on a wet chemical and a bottom-up approach, have been
proved to be efficient and suitable in preparing various ZnO
nanostructures due to their low growth temperature, cost effec-
tiveness, and potential for mass production. Hitherto hydrothermal
decomposition [14], solvothermal decomposition [15], liquid
ultrasonication [16], free surfactant microwave [17], solid state

http://dx.doi.org/10.1016/j.jallcom.2015.05.242
0925-8388/© 2015 Elsevier B.V. All rights reserved.
426 A. Diallo et al. / Journal of Alloys and Compounds 646 (2015) 425e430
chemistry [18], solution plasma [19], electrochemical reaction [20],
and solegel process have been employed to synthesize nano-scaled
ZnO.
The ZnO synthesis physical approach does require, in general, a
non cost-effective vacuum based infrastructure while limited in
terms of large-scale production. The chemical route has the
disadvantage of using chemical compounds/organic solvents as
reducing agents which can be toxic as well as not easy in treatment
of the waste end product. The so called “Green nano-synthesis”
approach which is based on using ecofriendly reagents or biogenic
processes, reduces the pollution risk at source level and avoids
waste rather than treat or clean it up after it is formed. More
accurately, green synthesis processes whereby the precursor of the
nano-material to be synthesized is reduced effectively via a
biochemical interaction with active compounds of the natural ex-
tracts, is gaining momentum [21,22].
This contribution reports on the synthesis and the main physical
properties of nano-scaled pure ZnO particles engineered for the 1st
time by an entirely green chemistry process using A. linearis's
natural extract as an effective chemical reduction agent without
addition of any acid or base standard component.
2. Synthesis: green process via A. linearis' natural extract
A. linearis' natural extract was used to reduce several Zinc based
salts including ZnNO3, and ZnCl2, as well as Zn-Ammonium hydrate
based precursors. This communication focuses on the green
reduction of ZnNO3 hexahydrate precursor as a proof of concept of
synthesis of single phase ZnO nanoparticles. A. linearis of the family
Fabaceae, also known as Rooibos, is a plant which is originally
found in the Southern Africa region. As summarized in Fig. 1, A.
linearis' extract contains, among others, two unique phenolic
compounds, namely aspalathin, dihydrochalcone C-glucoside, and
aspalalinin, a cyclic dihydrochalcone. Other major phenolic com-
pounds include flavones (orientin, isoorientin, vitexin, isovitexin,
luteolin, chrysoeriol), flavanones (dihydro-orientin, dihydro-
Fig. 1. Structure of the major bioactive molecular compounds within the Aspalathus linearis natural extract.
isoorientin, hemiphlorin) and flavonols (quercetin, hyperoside,
isoquercitrin, rutin). It is established that Aspalathin, which is a rare
CeC dihydrochalcone glycoside, and the two structurally related
chalcones (nothofagin and aspalalinin) are the most bioactive
compounds [23,24].
Dried A. linearis' flowers were cleaned thoroughly with cold de-
ionized H2O. Following a drying phase under sunny conditions at
ambient temperature, the powder were submitted to a grinding
phase. 5 A. linearis extract solutions were prepared in a fixed vol-
ume of de-ionised H2O each (300 ml, 25
C) for 48 h. The duration
of 48 h was considered to ensure the maximum extraction of the
bioactive compounds from the A. linearis ground powders. The
initial mass of the A. linearis powders dissolved in the de-ionized
H2O, were 0.5, 2, 4, 6 and 8 g. Each of the extract brown solutions
was filtered to eliminate residual solids if any. As Zinc precursor,
analytical grade reagent Zn(NO3) 6H2O from SigmaeAldrich was
used and preferred relatively to other salts (Chloride, sulfate, … .) in
view of the room temperature dissolution. A fixed amount of zinc
nitrate (3 g) was dissolved in each of the above mentioned solu-
tions. More precisely, the 5 A. linearis solutions named S1, S2, S2, S3,
S4 and S5 were prepared. This is intended to identify the threshold
concentration of the A. linearis necessary to reduce the full
considered Zinc nitrate precursor. As it is highlighted in the
experimental section, S4 was found to be the threshold concen-
tration from which the decomposition of the Zn nitrate precursor is
complete.
3. Results and discussion
3.1. Morphology & microscopy observations
Following the preparation phase described above, each of the
solutions Si was heated in capped bottles for 2 h (±9 min) at 80
C
(±5
C). A dark colored deposit consisting of fine particles appeared
for each of the concentrations. Fig. 2 reports typical Transmission
Electron Microscopy (TEM) and High Resolution Transmission
 A. Diallo et al. / Journal of Alloys and Compounds 646 (2015) 425e430 427

Fig. 2. HRTEM of the Zinc oxide nanoparticles (a) with their size distribution (b) and a typical electron diffraction pattern (c).

Electron Microscopy (HRTEM) observations on such dark particles' avoid charge effects) and K as well as C originating from the A. lin-
deposit. For the HRTEM, a Jeol JEM 4000EX electron microscopy earis, no other elements are observed except Zn and O in the case of
unit with a resolution limit of about 0.12 nm, equipped with a Gatan nanoparticles synthesized using extract solutions S4 and S5 while
digital camera, was used. Fig. 2a, shows that the dark deposits additional N peaks were observed in the EDS spectra of those syn-
consist of non-agglomerated quasi-spherical in shape nano- thesized using extract solutions S1, S2 and S3. Hence, one could
particles. Following a digitization phase of various images such as conclude that the chemical reduction of the hydrated Zn(NO3)2
Fig. 2a, the average diameter of the nanoparticles ranges from 1 to
8.5 nm as estimated by fitting the histogram data with a Gaussian
distribution centered at 〈fparticle〉 ~4.08 nm with 0.08 nm of stan-
dard deviation (Fig. 2b.). To conclude on the degree of crystallinity
of the nanoparticles, several HRTEM and electron diffraction anal-
ysis were carried out. From such observations, it was noticed that,
statistically, the major of the nanoparticles were amorphous as
reported in the Selected Area Electron Diffraction patterns SAED of
Fig. 2c. As reported below, this corroborates with the X-rays
diffraction analysis for the non heat-treated initial nanopowders.
Then each solution Si was purified via 3 times repeated centrifu-
gation at 1000 rpm for 10 min. A thermal annealing at 300
C under
air for 2 h was required to crystallize the nanoparticles without
affecting significantly their average size.

3.2. Elemental analysis

Fig. 3 shows a typical Energy Dispersive X-Ray Spectroscopy

(EDS) spectrum collected with an Oxford instruments X-Max solid
state Silicon drift detector operating at 20 keV on the annealed
nanopowders Si. Excluding Au and Pd from the coating phase (to Fig. 3. Typical EDS profile of the annealed Zinc oxide nanoparticles.
428 A. Diallo et al. / Journal of Alloys and Compounds 646 (2015) 425e430
precursor is complete in the case of solutions S4 and S5. Thus, the
solution S4 which consists of 6 g in 0,4 l of A. linearis can be
considered as the threshold concentration. For the deposits in so-
lutions S4 and S5, the average Zn/O atomic ratio deduced from the
EDS studies, is about 0.47/0.12. This, within the bar error, is
consistent with the theoretical value of atomic ration of ~1/1 i.e ZnO.
No other element has been detected so far, indicating, a priori, the
significant chemical purity of the formed Zincite nanoparticles
following the preparation and final filtration protocol described
above.
3.3. Structural & crystallographic analysis
As mentioned previously, the as prepared Zincite nanoparticles
synthesized by this green process of reaction via the bioactive
compounds of A. linearis natural extract, are generally amorphous, a
heat treatment is necessary to induce their crystallization. The
various heat treatments in air indicated that the threshold
annealing temperature was about 300
C (±5
C) during 2 h
(±9 min). Indeed, this threshold value was enough to induce a
significant crystallization of the ZnO nanoparticles. As established,
the crystal structures exhibited by ZnO are wurtzite, Zinc blende,
and rocksalt (or Rochelle salt). The standard conditions stable phase
is the wurtzite structure which has a hexagonal unit cell with two
lattice parameters 〈abulk〉 and 〈cbulk〉 in the ratio of 〈abulk〉/
〈cbulk〉 ¼ 1.633. This room temperature stable phase belongs to the
space group P63mc in the HermanneMauguin notation. As shown
in Fig. 4’s inset, it is composed of two interpenetrating hexagonal
close packed sublattices, each of which consists of one type of atom
displaced with respect to each other along the threefold c-axis. The
X-Rays Diffraction (XRD) pattern of the annealed nanoparticles
synthesized with the extract's concentration S4, is shown in Fig. 4
and the Miller indices are indicated for each Bragg peak. All the
diffraction peaks are indexed to the standard hexagonal wurtzite
structure of ZnO. The deduced lattice constants are
〈aexp〉 ¼ 0.319 nm and 〈cexp〉 ¼ 0.518 nm (〈cexp〉/〈aexp〉 ¼ 1.623),
which fits with the JCPDS file of ZnO (JCPDS number 36-1451).
While no other Zn compound was detected highlighting the purity
of the synthesized Zincite (At least at the detection limit of XRD),
there in no favored texture of the ZnO crystals, specifically towards
the standard (002). Likewise, one can notice that all the Bragg peaks
are quite broad with a width at half maximum 〈DQ1/2〉~1 deg
sustaining the nano-size of the formed ZnO even after the thermal
annealing. The Debye-Scherrer approximation allows to estimate
the average size of the annealed ZnO nanoparticles which is found
Fig. 4. Room temperature XRD profile of the annealed ZnO nanoparticles.
to be 〈fparticles〉 ~12.5 nm (Table 1).
3.4. Vibrational properties
In its hexagonal structure with P63mc symmetry of ZnO, the
group theory predicts eight sets of phonon normal modes at the G
point, namely, 2A1, 2E1, 2B1, and 2E2. Among them, one set of A1 and
E1 modes are acoustic, while the remaining six modes, namely, A1,
E1, 2B1, 2E2, are optical modes. Fig. 5 reports the room temperature
Raman spectrum collected using the Argon laser green excitation
lexc ¼ 514 nm. More precisely, Fig. 5 shows the spectrum of the
annealed nanoparticles synthesized with the extract's concentra-
tion S4. One can distinguish 5 major peaks which are approximately
centered at ~326.1, ~379.6, ~435.8, ~574.2, and ~829.4 cm1. The
peaks at ~326.1, ~379.6 and ~431.8 cm1 are attributed to the 2nd
order Raman scattering arising from 3E2H-E2L, A1(TO) and E2H
vibrational modes [25]. Yet assymetric, the E2H mode is a finger-
print of the degree of crystallinity of the wurtzite ZnO annealed
nanoparticles. The broad mode centered ~574.2 cm1 is assigned to
the E1(LO) mode, which is defects induced: Oxygen vacancies and
Zinc interstitials [26]. Although the possible mode centered at
~829.4 cm1 is potentially a vibrational mode, it is difficult to
attribute as it is within the background level.
3.5. Surface properties
To validate once more the wurtzite nature and the chemical
purity of the ZnO nano-crystallites synthesized by green reduction
of the Zinc nitrate hexahydrate by the A. linearis natural extract, X-
Rays Photoemission spectroscopy (XPS) were carried out on the
optimized annealed sample. The XPS investigations were acquired
using a constant 50 eV pass energy mode, in 0.1 eV increments at a
50 ms dwell time with the signal averaged for at several regular
scans. The XPS system was equipped with a dual Mg KaeAl Ka
anode for photoexcitation. Fig. 6 shows the typical XPS spectrum of
the annealed ZnO nanoparticles (300 ± 5
C, 2 h± 9 min) corre-
sponding to the threshold solution of A. linearis concentration S4.
The wide scan exhibited the major Zn and O peaks only and hence
sustaining the chemical purity of the surface of the Zinc oxide
nanoparticles. Fig. 6 focuses on the characteristic Zn2p and O1s
peaks and corresponding binding energies. The observed 2p1/2 and
2p3/2 of Zn which originates from a strong spin-orbit coupling [27],
are centered at 1021.2 and 1044.3 eV corresponding to a binding
energy of 23.05 eV in agreement with published literature [28e30].
The deconvolution of the O1s which is attributed to the O2 ions in
the wurtzite ZnO structure, exhibits 3 major peaks centered at
529.3, 530.1 and 531.1 eV. According to the literature, they originate
from surface defects and chemisorbed Oxygen respectively [31].
The Zn2p and O1s regions are consistent with stoichiometric ZnO. As
a pre-conclusion, one can deduce that the Zn atoms within the pure
Zincite nano-crystals are the oxidation state 2þ.
3.6. Defects distribution & nature
As a follow up of the EDS, XRD, Raman and XPS investigations,
room temperature photoluminescence (PL) studies were conducted
to estimate the nature and the density of the defects and ion de-
ficiencies if any. The excitation wavelength lexc ¼ 325 nm from a
HeeCd laser source was used to conduct the room temperature PL
measurements. Fig. 7 reports the PL spectrum of the annealed ZnO
nano-crystals (300 ± 5
C, 2 h± 9 min) corresponding to the
reducing solution of A. linearis concentration S4. One can distin-
guish the relatively sharp emission centered at about ~377.6 nm
due to the free excitonic recombination between the top of the
valence band and the bottom of the conduction band (caused by the
 A. Diallo et al. / Journal of Alloys and Compounds 646 (2015) 425e430 429

Table 1
Major XRD values and deduced nanoparticles' characteristics.

(hkl) qbulk(rad) qexp(rad) dhklbulk (Å) dhklexp (Å) dhklexpdhklbulk/dhklbulk FWHM (rad) 〈 f 〉 (nm)

(100) 0.2772 0.2777 2.8143 2.8091 0.0018 0.0083 17.17

(002) 0.3003 0.3012 2.6033 2.5961 0.0027 0.0103 13.98
(101) 0.3163 0.3166 2.4759 2.4741 0.0007 0.0117 12.46
(102) 0.4148 0.4155 1.9111 1.9080 0.0016 0.0108 13.99
(110) 0.4939 0.4947 1.6247 1.6224 0.0014 0.0115 13.69
(103) 0.5485 0.5494 1.4771 1.4751 0.0013 0.0123 13.23
(200) 0.5792 0.5819 1.4071 1.4013 0.0041 0.0274 6.05
(112) 0.5930 0.5941 1.3781 1.3760 0.0015 0.0088 19.03
(201) 0.6030 0.6019 1.3582 1.3603 0.00152 0.0718 2.34

Fig. 5. Raman spectrum of the annealed ZnO nanoparticles. Fig. 7. Room temperature photoluminescence of the annealed ZnO nanoparticles.

Fig. 6. Zn2p X-rays photoemission spectroscopy spectrum of the annealed ZnO nanoparticles.
430 A. Diallo et al. / Journal of Alloys and Compounds 646 (2015) 425e430
large exciton binding energy of ZnO (~60 mV)) [32]. There is a broad
emission within the spectral range of 400e700 nm. The integrated
intensity of this broad emission is far larger relatively to the exci-
tonic emission; at least by a factor of 7. This indicates the presence
of a significant surface or/and volume defects [33]. The Gaussian
deconvolution of the broad emission allows to identify at least 5
type of emissions ranging from the bleu to the red. The spectral
positions of the maximum and the width at half maximum of the
various Gaussians are: lmax (Dl1/2) are ~443.4 (33.1), ~481.9 (51.7),
~529.7 (65.8), ~675.8 (94.5), and ~808.3 nm (142.6 nm). Generally
the visible bands (Deep level emission) are considered as caused by
impurities and structure defects [34]. In view of the XPS and EDS
results, there are no impurities at least at the detection limit of both
techniques. Hence the visible bands are caused by structure defects
in the Zincite nanoparticles. The peak at 443.4 nm is ascribed to
interstitial Zinc (Zni) [35], while the peak at 481.9 nm remains with
Zinc vacancy (VZn) [36]. Although there have been controversies
for a long time about the origin of the peak at 529.7 nm, it is usually
assigned to Oxygen antisite (OZn) [37] and Oxygen Vacancy (VO)
[38]. The orange emission centered at about 675.8 nm is also
attributed to (VO) [39]. It represents a common feature in ZnO
samples prepared by electrochemically [40], hydrothermally [41],
and spray pyrolysis methods [42]. The orange emission is
commonly attributed to oxygen interstitials, which is supported by
the reports of decreasing or vanishing of orange contribution after
annealing under vacuum or in a H2/Ar mixture Cross et al. [43] and
Green et al. [44].
As a follow up, we will explore via adequate characterization
techniques the physical and chemical processes driving the reac-
tion of the natural extract of the Hibiscus Sabdarifa and the Zn
nitrate precursor and their dynamic in view of identifying the exact
mechanisms of formation of the ZnO nanopraticles. Likewise,
several studies on their photonics, gas sensing and optoelectronic
properties will be performed and compared to previous literature
results [45e55].
4. Conclusions
The synthesis of high purity crystalline ZnO quasi-spherical
nanoparticles by green process using the natural extract of A. lin-
earis as an effective reduction/oxidizing chemical agent was
demonstrated for the 1st time. A thermal annealing at 300 ± 5
C
during 2 h± 9 min under normal air conditions allows the obtention
of crystallized single phase ZnO nanoparticles as substantiated by
EDS, Raman, XPS and PL investigations. The follow up study will
consist of identifying the mechanism and the dynamic of formation
of the ZnO nanoparticles during the interaction of the Zn salt pre-
cursor and the A. linearis extract compounds.
Acknowledgments
This research program was generously supported by grants from
the National Research Foundation of South Africa (NRF), (NRF 2014-
TANZ SA-MM) iThemba LABS, the UNESCO-UNISA Africa Chair in
Nanosciences & Nanotechnology, (U2ACN2 2014-MM Y1) the Or-
ganization of Women in Science for the Developing World
(OWSDW) (NRF 2014-iTl MM Y2) and the Abdus Salam ICTP (ICTP
2014-ICTP Network 62) via the Nanosciences African Network
(NANOAFNET) as well as the African Laser Centre (ALC) (ALC 2014-
TANZ SA-MM Y1) including the French Centre National pour la
Recherche Scientifique, to whom we are grateful.
References
[1] H. Morkoc, U. Ozgur, Wiley-VCH (2007).
[2] R.G. Gordon, Mater. Res. Soc. 25 (2000) 52.
[3] D.S. Ginley, C. Bright, Mater. Res. Soc. 25 (2000) 15.
[4] L. Vayssieres, K. Keis, A. Hagfeldt, S.E. Lindquist, Chem. Mater. 13 (2001)
4395e4398.
[5] J. Sithole, B.D. Ngom, S. Khamlich, E. Manikanadan, N. Manyala, M.L. Saboungi,
D. Knoessen, R. Nemutudi, M. Maaza, Appl. Surf. Sci. 258 (2012) 7839e7843.
[6] J. Qiu, B. Weng, L. Zhao, C. Chang, Z. Shi, X. Li, H.-K. Kim, Y.-H. Hwang,
J. Nanomater. (2014) 1e11, http://dx.doi.org/10.1155/2014/2814 (Article ID
281461).
[7] X.H. Zhang, Y.C. Liu, X.H. Wang, J. Phys. Condens. Matter 17 (2005)
3035e3042.
[8] J.Y. Park, Y.S. Yun, Y.S. Hong, H. Oh, S.S. Kim, Appl. Phys. Lett. 87 (2005) 1e3.
[9] M.T. Chen, J.M. Ting, Thin Solid Films 494 (2006) 250e254.
[10] Y. Sun, M.N.R. Ashfold, Nanotechnology 18 (2007) 24.
[11] Y.B. Li, Y. Bando, T. Sato, K. Kurashima, Appl. Phys. Lett. 81 (2002) 144e146.
[12] B.D. Yao, Y.F. Chan, N. Wang, Appl. Phys. Lett. 81 (2002) 757e759.
[13] Z.W. Pan, Z.R. Dai, Z.L. Wang, Science 291 (2001) 1947e1949.
[14] S. Yang, J. Wang, D. Wang, J. Yang, Appl. Surf. Sci. 319 (2014) 211e215.
[15] G. Xu, X.L. Wang, G.Z. Liu, Appl. Surf. Sci. 329 (2015) 137e142.
[16] Q.L. Ma, R. Xiong, B. Zhai, Y.M. Huang, Appl. Surf. Sci. 324 (2015) 842e848.
[17] V.V. Shinde, D.S. Dalavi, S.S. Mali, C.K. Hong, J.H. Kim, P.S. Patil, Appl. Surf. Sci.
307 (2014) 495e502.
[18] M. Pudukudy, Z. Yaakob, Appl. Surf. Sci. 292 (2014) 520e530.
[19] G. Saito, Y. Nakasugi, T. Yamashita, T. Akiyama, Appl. Surf. Sci. 290 (2014)
419e424.
[20] J. Yang, G. Liu, J. Lu, Y. Qiu, S. Yang, Appl. Phys. Lett. 90 (2007) 10.
[21] B. Dias Ribeiro, I. Marrucho, L. Gonçalves, M.A.Z. Coelho, BioMed Res. Int. 2014
(2014) 1e2, http://dx.doi.org/10.1155/2014/590586 (Article ID 590586).
[22] P. Mohanpuria, N.K. Rana, S.K. Yadav, J. Nanopart. Res. 10 (2008) 507e517.
[23] E. Joubert, D. de Beer, S. Afr. J. Bot. 77 (2011) 869e886.
[24] M. Aragone s, G. Camps, J. Alonso-Villaverde, C. Mene ndez, J.A. Micol,
V. Segura-Carretero, A. Joven, J. Phytomed. 18 (2011) 414e424.
[25] L. Zhang, J. Zhao, J. Zheng, L. Li, Z. Zhu, Appl. Surf. Sci. 258 (2011) 711e718.
[26] C.M. Ghimbeu, J. Schoonman, M. Lumbreras, M. Siadat, Appl. Surf. Sci. 253
(2007) 7483e7489.
[27] N.L. Tarwal, A.V. Rajgure, A.I. Inamdar, R.S. Devan, I.Y. Kim, S.S. Suryavanshi,
Sens. Actuators A Phys. 199 (2013) 67e73.
[28] N.H. Al-Hardana, A. Jalara, M.A. Abdul Hamid, L.K. Keng, R. Shamsudin,
B.Y. Majlis, Sens. Actuators B 203 (2014) 223e228.
[29] J. Das, S.K. Pradhan, D.R. Sahu, D.K. Mishra, S.N. Sarangi, B.B. Nayak, Phys. B
Condens. Matter 405 (2010) 2492e2497.
[30] R.K. Sahu, K. Ganguly, T. Mishra, M. Mishra, R.S. Ningthoujam, S.K. Roy,
J. Colloid Interface Sci. 366 (2012) 8e15.
[31] M. Chen, X. Wang, Y.H. Yu, Z.L. Pei, X.D. Bai, C. Sun, Appl. Surf. Sci. 158 (2000)
134e140.
[32] N.K. Singh, S. Shrivastava, S. Rath, S. Annapoorni, Appl. Surf. Sci. 257 (2010)
1544e1549.
[33] L. Zhang, J. Zhaoa, J. Zheng, L. Li, Z. Zhu, Appl. Surf. Sci. 258 (2011) 711e718.
[34] N.Y. Garces, L. Wang, L. Bai, N.C. Giles, L.E. Halliburton, G. Cantwell, Appl. Phys.
Lett. 81 (2002) 622.
[35] P.K. Samanta, S.K. Patra, P. Roy Chaudhuri, Phys. E 41 (2009) 664e667.
[36] K.T. Roro, J.K. Dangbegnon, S. Sivaraya, A.W.R. Leitch, J.R. Botha, J. Appl. Phys.
103 (2008) 053516.
[37] H. Hu, X. Huang, C. Deng, X. Chen, Y. Qian, Mater. Chem. Phys. 106 (2007)
58e62.
[38] C.H. Tsai, W.C. Wang, F.L. Jenq, C.C. Liu, M.P. Houng, J. Appl. Phys. 104 (2008)
053521.
[39] Z. Fan, P. Chang, J.G. Lu, E.C. Walter, R.M. Penner, C. Lin, H.P. Lee, Appl. Phys.
Lett. 8 (2004) 6128.
[40] M.J. Zheng, L.D. Zhang, Chem. Phys. Lett. 363 (2002) 123e128.
[41] T. Sekiguchi, K. Haga, K. Inaba, J. Cryst. Growth 214e215 (2000) 68e71.
[42] S.A. Studenikin, N. Golego, M. Cocivera, J. Appl. Phys. 84 (1998) 2287e2289.
[43] R.B.M. Cross, E.M.S. Narayanan, Nanotechnology 16 (2005) 2188e2192.
[44] L.E. Green, M. Law, J. Goldberger, Angew. Chem. Int. Ed. 42 (2003).
[45] M. Maaza, B.D. Ngom, M. Achouri, E. Manikandan, Vacuum 114 (2015)
172e187.
[46] B.D. Ngom, O. Sakho, S. Ndiaye, M. Maaza, A.C. Beye, EPJ Appl. Phys. 55 (2011)
20501.
[47] B.D. Ngom, M. Chaker, N. Manyala, M. Maaza, A.C. Beye, Appl. Surf. Sci. 257
(2011) 6226e6232.
[48] B.D. Ngom, O. Sakho, N. Manyala, M. Maaza, A.C. Beye, Appl. Surf. Sci. 255
(2009) 7314e7318.
[49] B.D. Ngom, T. Mpahane, N. Manyala, M. Maaza, A.C. Beye, Appl. Surf. Sci. 255
(2009) 4153e4158.
[50] P.H. Sechogela, L. Kotsedi, M. Nkosi, K. Bharuth-Ram, M. Maaza, Surf. Rev. Lett.
21 (2014) 1450012.
[51] M. Khenfouch, M. Baitoul, M. Maaza, Opt. Mater. 34 (2012) 1320e1326.
[52] A.C. Nwanya, P.R. Deshmukh, R.U. Osuji, C.D. Lokhande, F.I. Ezema, Sens. Ac-
tuators B Chem. 206 (2015) 671e678.
[53] M. Khenfouch, M. Baïtoul, M. Maaza, Opt. Mater. 36 (2013) 27e30.
[54] E. Manikandan, V. Murugan, G. Kavitha, P. Babu, M. Maaza, Mater. Lett. 131
(2014) 225e228.
[55] A.C. Nwanya, P.R. Deshmukh, R.U. Osuji, M. Maaza, C.D. Lokhande, F.I. Ezema,
Sens. Actuators B Chem. 206 (2015) 671e678.