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CERAMICS
INTERNATIONAL
Available online at www.sciencedirect.com
Ceramics International 40 (2014) 77377743
Facile synthesis of different morphologies of Te-doped ZnO nanostructures
Farid Jamali-Sheini
a,n
, Ramin Youse
b
, M.R. Mahmoudian
c
, Nabeel Ali Bakr
d
,
Abdolhossein Saaedi
e
, Nay Ming Huang
f
a
Department of Physics, Ahwaz Branch, Islamic Azad University, Ahwaz, Iran
b
Department of Physics, Masjed-Soleiman Branch, Islamic Azad University (I.A.U), Masjed-Soleiman, Iran
c
Department of Chemistry, Shahid Sherafat, University of Farhangian, Tehran 15916, Iran
d
Department of Physics, College of Science, University of Diyala, Diyala, Iraq
e
Department of Electrical Engineering, Bushehr Branch, Islamic Azad University (I.A.U), Bushehr, Iran
f
Low Dimensional Materials Research Center, Department of Physics, Faculty of Science, University of Malaya, Kuala Lumpur 50603, Malaysia
Received 9 December 2013; received in revised form 23 December 2013; accepted 24 December 2013
Available online 10 January 2014
Abstract
Te-doped ZnO nanostructures were synthesized by an annealing (vaporsolid) process under ambient conditions, and characterized in terms of
their morphological, structural, compositional and optical properties. The structural and morphological characterizations revealed that the
synthesized nanostructures were well-dened multipods, needles and spherical particles, and possessed well-crystalline ZnO wurtzite hexagonal
phase. Also, in the X-ray diffraction studies, the presence of a shift in the peak positions towards a lower angle, and a decrease in the intensity,
with an increase in the Te concentration, as compared to the undoped ZnO, were observed. The chemical composition conrmed the presence of
Te, in the case of multipod and needle morphologies. The effect of doping on the crystalline quality and optical properties was also investigated,
by using photoluminescence (PL) and Raman spectrometers. The Raman results demonstrated that the doped ZnO nanostructures had a lower
crystalline quality than the undoped ZnO. Moreover, the PL results showed a decrease in the band gap for the doped ZnO nanostructures, in
comparison to the undoped ZnO. A possible growth mechanism was also proposed.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Te-doped ZnO; Nanostructures; Photoluminescence; Raman spectroscopy; Growth mechanism
1. Introduction
Zinc oxide (ZnO) is an interesting metal oxide with a direct
wide band gap (3.3 eV) and strong excitonic binding energy
(60 meV). Nanoscale ZnO has been found to be a promising
material for different applications, such as electronic and
optical devices [16]. Additionally, ZnO is naturally an n-
type semiconductor, owing to the presence of native defects,
such as oxygen vacancy and zinc interstitial. These defects
induce deep levels into the band gap and can affect the
physical properties. Previous studies have shown that doping
with appropriate elements is a powerful method to tailor the
electrical and optical properties, facilitating the fabrication of
many optoelectronic devices. Our experience showed that the
ZnO, decorated with suitable elements, modies the optical
transitions by creating localized impurity levels [58]. Gen-
erally, selective elements as dopant materials in ZnO can be
classied into two groups of materials: one group can be
substituted for Zn; and the other can be substituted for O.
These different types of doping materials can exhibit different
optical properties for ZnO, owing to the different treatments of
Zn and O in the ZnO structure. The literature shows that much
attention has been paid to cationic doping in ZnO nanostruc-
tures. On the other hand, less attention has been paid to the
anionic doping effect on the morphology of ZnO nanostruc-
tures and their optical properties.
Tellurium as a chalcogen element could serve as an anionic
dopant in ZnO. Therefore, this element can be used as a
substitution element for O in ZnO lattice. It is known that,
usually, a photoluminscnce study of ZnO structures shows two
peaks: one peak in the ultraviolet region; and another peak in
the visible region (deep level emission; DLE). It has been
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n
Corresponding author. Tel.: 98 611 3348420 24; fax: 98 611 3329200.
E-mail addresses: faridjamali2003@yahoo.com,
faridjamali@iauahvaz.ac.ir (F. Jamali-Sheini).
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suggested that the DLE corresponds to the singly ionized
oxygen vacancy in ZnO, and results from the recombination of
a photo-generated hole with the singly ionized charge state of
this defect [9]. Therefore, it is expected that Te can change the
optical behavior of ZnO in the visible region. Recently,
Iribarren et al. reported the effect of Te atoms on the optical
properties of nanostructured ZnO [10,11]. The results showed
that Te atoms have the effect on O vacancy passivation in the
ZnO structure, and the O vacancy can be reduced [10,11].
Although the different synthesis methods have been developed
to fabricate doped and undoped ZnO nanostructures, testing a
selected element, along with a simple, quick and economical
method for the preparation of doped ZnO nanostructures, is
important. In addition, many elements have been checked for
their physical properties as dopants in ZnO nanostructures,
from the literature survey, less work has been performed to
date on the optical properties of ZnO nanostructures modied
by Te atoms.
Therefore, the purpose of this report is twofold: to report a
new and rare experimental condition to synthesize different
TeZnO nanostructures; and to discuss the effect of different
morphologies of TeZnO nanostructures on their optical
properties. Although our understanding of this experimental
condition is needed in order to be complete, this study will
provide useful insights into the understanding and design of
different conditions to achieve various morphologies. On this
basis, the synthesis of TeZnO nanostructures from Zn and
TeO
2
powders by direct heating in a box furnace is reported.
Different analysis techniques have been used to study the
properties of obtained materials.
2. Experimental details
2.1. Synthesis
The synthesis of TeZnO nanostructures was done on a Si
substrate in ambient conditions in a box furnace. The growth
was performed inside a crucible by arranging a vertical
ceramic tube and a cap as a synthesis reactor, without proving
a complicated reactor. The schematic synthesis reactor is
depicted in Fig. 1. First, Si(1 1 1) substrate was cleaned
ultrasonically, using ethanol and de-ionized water. It was then
etched lightly with an HF (43%) and de-ionized water mixture
(1:10) for about 10 min, to remove the native oxide layer. In
addition, all parts of the reactor were cleaned ultrasonically
using acetone, ethanol and distilled water for 5 min each, and
dried in air. The mixed commercial powders of Zn (Merck,
1 g; 99.9%) and TeO
2
(Merck, 0.5 g; 99%) were placed at the
bottom of a ceramic tube, and the Si substrate was kept at the
other opening side. The cap of the crucible was xed before
starting the heating. The temperature of furnace was pro-
grammed to 1000 1C. Total heating duration was 2.5 h. After
cooling to room temperature, the ceramic reactor was removed
and the Si substrate was separated. The deposition was carried
out on the Si substrate and the inner side of ceramic crucible
cap. The lm grown on the Si substrate has good adherence,
but the lm deposited on the cap can be removed easily in the
form of a sheet. The characterization was performed on the
lms grown on the Si substrate and cap. At least three
specimens were synthesized under identical experimental
conditions for each deposition, and characterized using various
analytical techniques, in order to check the reproducibility and
repeatability of the results.
2.2. Characterization
The specimens were characterized using X-ray diffract-
ometer (XRD; PANalytical, X'Pert Pro MPD), scanning
electron microscope (SEM; LEO, 1455VP), The elemental
composition was obtained using an energy-dispersive X-ray
spectrometer (EDS) attached to the SEM. The optical proper-
ties were investigated using Raman and photoluminescence
(PL) spectra, which were carried out at room temperature.
Raman spectra were recorded using a spectrophotometer
(BRUKER, SENTERRA) over a wavenumber range of
250700 cm
1
. The PL spectra were measured using a photo-
luminescence spectrometer (Perkin Elmer, LS 55), with a
Xenon lamp as a light source.
3. Results and discussion
3.1. Structural, morphological and compositional analysis
The XRD patterns of as-synthesized materials grown on the
different zones of the growth reactor (i.e. on the Si substrate
and inner side of ceramic crucible cap) are shown in Fig. 2.
The patterns of the specimens indicate that all the peaks are in
good agreement with the JCPDS data belonging to hexagonal
ZnO phase (Card No. 80-0075). Apart from ZnO characteristic
peaks, no peaks corresponding to Te, Zn or their complex
oxides could be detected. This result shows that the obtained
materials do not have any phase segregation or secondary
phase formation, as well as the incorporation of Te into the
ZnO lattice. The (1 0 0) and (1 0 1) peaks appear with a
maximum intensity for all the specimens. The (1 0 0) peak was
located at 31.891 for the lm grown on the cap, and at 31.831
Fig. 1. Schematic illustration of synthesis reactor.
F. Jamali-Sheini et al. / Ceramics International 40 (2014) 77377743 7738
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for the lm obtained on the Si substrate. Also, the (1 0 1) peak
was centered at 34.541 and 34.491 for the lms grown on the
cap and Si substrate, respectively. It is found that the peaks
corresponding to the lm grown on the Si substrate showed a
shift towards a lower angle compared with the other one [12].
These shifts in peak position reect that Te is incorporated into
the ZnO matrix. It can be expected that with the increase in Te
concentration the crystalline quality of obtained materials
declines gradually. It is important to note that the radius of
Te and O ions in the wurtzite ZnO crystal is expected to be r
(Te
2
) 2.07 and r (O
2
) 1.40 . The large radius of Te
as compared with O ions can deform the ZnO lattices.
Therefore, the TeZnO nanostructures exhibit a slightly lower
angle shift of (1 0 0) and (1 0 1) peaks from the material grown
on the cap by 0.051, which is possibly due to the larger
radius of Te.
Fig. 3 shows typical SEM images of as-synthesized materials
on the different zones of the growth reactor. It is found
that there are three types of morphologies on the Si substrate
and cap of the reactor. One kind of growth is shown in Fig. 3(a)
and (b), which consists of well-dened multipode morphology
Fig. 2. XRD patterns of as-synthesized lms grown on different zones of the
synthesis reactor.
Fig. 3. SEM micrographs of as-synthesized materials on the different zones of the synthesis reactor.
F. Jamali-Sheini et al. / Ceramics International 40 (2014) 77377743 7739
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composed of nanorods. The low magnication SEM image
reveals similar morphological distribution, and does not show
other morphologies. The average diameter of the rods is about
80 nm, and the length is 200 nm. It is also important to note that
all rods have a at top surface. This type of growth was on the
entirety of the substrate except at the edges close to the opening
gap. The second type of as-synthesized materials has needle
morphology, as depicted in Fig. 3(c) and (d). As can be seen in
the SEM images, the needhes are completely straight, with
non-aligned arrays, and are tapered with a tip diameter of
1075 nm and a base diameter less than 100 nm. This type of
growth was in the vicinity of the opening gap, with a spread of
3 mm. The change in the morphology from the center to edge
should be a result of the increased concentration of ZnO vapor,
which causes ZnO nuclei to grow in the c-axis growth direction.
The third type of as-synthesized materials is spherical morpho-
logy, with diameters in the range of 20 to 100 nm, which is
shown in Fig. 3(e) and (f). Although the spherical morpho-
logy showed a wide variation in diameter, below 60 nm spheres
were dominant in our products. Fig. 4 demonstrates a schematic
sketch of the reactor and each zone of deposition. These
Fig. 4. Schematic illustration of synthesis reactor with morphological location
of each deposition zone.
Fig. 5. EDS spectra of the as-synthesized lms grown at: (a) the center; (b) the edge of the substrate; and (c) the inner side of the ceramic crucible cap.
F. Jamali-Sheini et al. / Ceramics International 40 (2014) 77377743 7740
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results suggest that the morphology could be varied with growth
process.
EDS analysis conrmed that the as-synthesized materials
were composed of Zn, O and Te only for the growth on the Si
substrate. From Fig. 5(a)(c), it is found that the rods, which
are grown at the center of the Si substrate, have little O
deciency, as compared with the needles formed at the edge of
substrate (i.e. percentage of O: 42 to 44%). In addition, the
percentage of Te is increased from the edge to the center of
substrate (i.e. 0.2 to 0.5%). It is interesting to note that the
obtained materials grown on the inner side of ceramic crucible
cap could not detect the Te element, and only showed the
presence of Zn and O with the proper stoichiometry. From
these results it can be concluded that the lm growth on Si
substrate is doped with Te, and is called Te-doped ZnO, and
the lm deposited on the inner side of the crucible cap is called
undoped ZnO. This observation is in good agreement with
the previous results on the effect of oxygen passivation on the
ZnO structure [10,11].
3.2. Raman and photoluminescence studies
The crystalline quality and the optical properties of Te-
doped ZnO nanostructures were examined by Raman and PL
measurements. Fig. 6 shows the Raman spectra of the TeZnO
nanostructures grown on the Si substrate and cap. Sharp and
strong peaks at 437.5 cm
1
in the spectra of all cases are
assigned to the Raman-active E
2
(high) mode, and is char-
acteristic of the hexagonal wurtzite phase of ZnO [13,14]. The
appearance of very small and suppressed peaks in the range of
581.5582 cm
1
in all cases, corresponding to the E
1L
mode,
is attributed to the presence of structural defects, such as
oxygen vacancies, zinc interstitial, free carriers and impurities
in the obtained materials [14,15]. Furthermore, the presence of
the two very weak peaks in the spectra located in the range of
331.5 and 380.5381.5 cm
1
are referred to as E
2H
E
2L
(multi-phonon) and A
1T
modes, respectively [15]. Addition-
ally, the peak centered at 521 cm
1
, in the case of multipode
rods and needle morphologies, is a result of the silicon
substrate. Generally, it was believed that the appearance of
the strong, and sharp Raman-active E
2
(high) mode and a very
suppressed and small E
1L
mode indicated that obtained
materials possessed good crystal quality with the wurtzite
hexagonal phase. Therefore, it is expected that the spherical
morphology (undoped ZnO) has a higher crystal quality.
Furthermore, in order to investigate the optical properties of
the obtained nanostructures, PL measurements at room tem-
perature were also performed, and that is depicted in Fig. 7.
Generally, the PL spectra of ZnO have two emission bands:
one is in the UV range (sharp band), which is associated with
the near band edge transition of ZnO, specically the
recombination of free excitons; the other is in the visible
range (broad band), which originates from electronhole
recombination at the deep level (DL), caused presumably by
oxygen and zinc vacancies, oxygen and zinc interstitials,
impurities, dopands and surface states [1619]. In these cases,
it can be observed that all of the measurements showed a
similar PL feature, with different intensities in the visible
region. A closer inspection in the UV region showed 2 nm
shifts in the obtained morphologies. On the other hand, there is
a red shift between multipodes and needles with respect to
spherical morphology. In the case of the visible region, it is
plausible to consider that the broad visible peak is composed
of three narrower peaks in the green, yellow and red emission
regions, which originated from different defect mechanisms.
Different visible emissions related to the presence of defects
appear in the obtained morphologies, which could be the result
of the different rate of growth process and dopant. Further-
more, it is well-known that the surface state is restricted on the
surface of the structure. Thus, the doped ZnO lms had
different morphologies because the surface-to-volume ratio
Fig. 6. Raman spectra of the as-synthesized lms grown on different zones of
the synthesis reactor.
Fig. 7. PL spectra of the as-synthesized lms grown on different zones of the
synthesis reactor.
F. Jamali-Sheini et al. / Ceramics International 40 (2014) 77377743 7741
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had different values, which, in turn, affected the PL results. In
addition, the EDS results show that the relative atomic
percentage of Te and oxygen deciency are higher in the
multipodes than in the needles, which suggests that the main
reason for the higher peak intensity in the visible region is the
presence of Te atoms and/or oxygen vacancies in the ZnO
nanostructures. To compare the optical properties of the
obtained morphologies, the ratio of UV/DL is the main factor.
The bigger ratio means a higher the crystalline quality.
Therefore, the multipodes morphology has a better relative
crystalline quality (grown at the center of the Si substrate), and
needle morphologies have a lower relative crystalline quality
(grown at the edge of the Si substrate). This might be a result
of the rapid growth rate of this morphology which is placed at
the edge of the Si substrate. It can be accepted that the
probability of the defects
0
formation, such as zinc and oxygen
interstitials/vacancies and/or dopands, etc. at this portion, can
be increased. Thus, faster growth rates in different places
introduced the defect levels, which contribute to the visible
region of PL spectra of ZnO nanostructures. Hence, it can be
concluded that the growth rate of needle morphology is high,
and the growth rate of multipode morphology is low. In
addition, a slight red shift in the peak position of the UV
emission for the needle morphology with the relative higher
intensity in the visible region could be attributed to the Te
doping, as well as to surface states. In fact, the PL results
conrm the Raman and XRD results.
3.3. Growth mechanism
Based on the XRD and EDS results, the following reaction
can be written for the doping process during the deposition of
Te-doped ZnO on the surface of the Si substrate:
Zn(s)-Zn(l)-Zn(g)
TeO
2
(s)-TeO
2
(l)-TeO
2
(g)
Zn(g) TeO
2
(g)-ZnO(g) Te(g)
ZnO(g) xTe(g)-ZnTe
x
O
(1x)
x/2 O
2
(g)
The comparison of the formation enthalpy of TeO
2
and ZnO
( 321 and 341.3 kJ mol
1
) conrmed that the dominant
phase is ZnO. This interpretation can be conrmed by the
XRD results. On the other hand, the EDS result showed the
existence of the Te element. Therefore, it can be proved that
the doping process was performed successfully. The compar-
ison of the Te dopant concentration with the variation of
morphology clearly shows that with the decrease in Te dopant
concentration, the rod morphology changes to the needle
morphology. The comparison of the melting point of ZnTe
and ZnO (1238 and 1975 1C, respectively) shows that the Te-
doped ZnO(g) can convert to solid phase immediately after
interaction with the surface of the Si substrate. On the other
hand, the size of the Si substrate was smaller than the area of
the ceramic tube, and it could not close the tube. In addition,
the EDS results show that the Te-doped ZnO concentration
decreased from the center to the edge of the Si substrate.
Therefore, by decreasing the temperature from the center to the
edge of the Si substrate the vapor pressure of Te-doped ZnO
was decreased. It is notable that by changing the substrate
type, the morphology of the deposited ZnO would be changed.
Therefore, it is clear that the morphology of deposited ZnO on
the surface of the ceramic is different from its morphology on
the surface of Si.
4. Conclusion
In a nutshell, a successful synthesis of Te-doped and undoped
ZnO nanostructures have been done by a simple method under
ambient conditions. The structural and morphological studies
conrmed that the synthesized materials are well-crystalline
wurtzite hexagonal phase and exhibit well-dened, different
morphologies. The optical investigation showed a decrease in
the band gap of doped ZnO nanostructures, compared with the
undoped ZnO. The results showed that the variation of growth
rate and presence of different concentrations of dopant were the
main reasons for the change in the morphology and tuning of the
optical properties. This method can be employed to open a way
to synthesize undoped and doped nanostructures in other metal
oxides.
Acknowledgements
F. Jamali-Sheini and R. Youse gratefully acknowledge the
Islamic Azad University, Ahwaz and Masjed-Soleiman Branches,
for nancial support of this research work. In addition, N.M.
Huang acknowledges obtaining a High Impact Research Grant
from the Ministry of Higher Education of Malaysia (UM.C/P/
HIR/MOHE/SC/21).
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