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Raman Spectroscopic Study of the ZnO Nanostructures

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 J Pak Mater Soc 2010; 4(1)

Raman Spectroscopic Study of the ZnO Nanostructures

Aurangzeb Khan
Institute of Physics and Electronics, University of Peshawar, Khyber-Pukhtunkhwa,
Pakistan, 25100.
Email: khan@upesh.edu.pk; Tel: +92-91-9216727,
Abstract
A variety of Zinc Oxide (ZnO) nanostructures such as nanowires, nanospheres,
nanorods, flower-like, tubules and tetrapods were synthesized via thermal evaporation
process using Zn and ZnO precursors in a tube furnace. The structural and optical
properties of the as grown structures were characterized by Scanning Electron
Microscopy (SEM) and Raman Spectroscopy. Raman spectroscopic results for the
nanostructures in comparison with the recent developed theory and well established
experimental data are reported. We have observed significant Raman shifts for these
ZnO nanostructures in the typical Raman-active modes assigned to ZnO. The main
peak known as E2(High), which is the finger print of wurtzite crystal structures, show
remarkable blue-shifts for these nanostructures when compared with the theoretical and
experimental results. The Raman shifts in the typical Raman-active modes is usually
reported towards the higher wave numbers which is regarded the characteristics of the
nanostructures. But we have also observed the Raman shifts towards lower wave
numbers for some of the typical Raman-active modes in various morphologies.
Keywords: Nanostructures, Raman Spectroscopy, Zinc Oxide, Vapor deposition

1. Introduction of this material suitable for device

Nanomaterials have attracted great applications with longer life7-8.
attention due to their potential
In order to understand this material,
applications in many fields such as
several groups have reported the
nano-scale electronic and optoelectronic
Raman spectroscopic analysis for ZnO
devices1-3. The study of the chemical nanostructures9-10 but very little has
and physical properties of various nano-
been done as far as the comparative
materials will result in further
study is concerned. Here, we report a
understanding of some of the basic
comparative study of the Raman spectra
issues about dimensionality. ZnO is a
of various kinds of nanostructures such
wide band gap semiconductor (~3.37 as nanowires, spheres, nanorods,
eV) with a large exciton binding energy
flower-like, tubular and tetrapods. We
(~60 meV i.e. much larger than room have compared the obtained spectra for
temperature ~26 meV) useful for stable
the said morphologies with the
device applications4-6. This material has
theoretically predicted one and with the
been considered a promising material
bulk counter parts. We believe that the
for short-wavelength, light-emitting, and
blue-shift in E2(High) is due to defects
gas sensing applications6. Furthermore,
and internal strains are due to different
ZnO has good thermal and chemical
growth directions.
stability, which make the nanostructures

Aurangzeb Khan: Raman Spectroscopic Study……… 5


2. Experimental
ZnO nanostructures are synthesized by
vapor-solid method, using a mixture of
high purity ZnO (99.0% min and -325
mesh) and graphite powders (99.0%
and -300 mesh) in a tube furnace. The
tube furnace is fitted with a quartz tube
(4 ft long and 3 inch wide) placed
horizontally in the furnace. A number of
silicon substrates are placed inside the
tube at the downstream end of the tube.
Ar gas is used at ~10-30 sccm to
transport vapors towards the substrates.
ZnO and graphite mixture is loaded in a
quartz crucible and placed in the middle
of the furnace tube at the hottest zone
and heated at 900-1100oC. The
substrates are kept in an area of
temperature gradient 900-200oC. The
experiments were usually allowed for
45-60 minutes. Usually a white and
bluish/grey product material is found on
substrates and the surrounding areas.
The nanostructures were characterized
by a JOEL JSM 5300 scanning electron
microscope (SEM) equipped with an
energy dispersive X-ray spectroscopy
(EDX), a Rigaku Geigerflex (2000
Watts) X-ray diffractometer (XRD) with
Cu Kα(0.154 nm) source. Raman
spectra were obtained using a Near-
Field Scanning Optical Microscope
imaging system (WiTECH α-SNOM)
integrated with Raman spectrometer,
with 532 nm laser light with Nd:YAG
laser as an excitation source. A 100X
objective lens was used, with a laser
spot size of ~ 500 nm11.
3. Results and Discussions
The morphologies of the nanostructures
are shown in Figure 1. Six different
kinds of nanostructures are shown i.e.
randomly oriented nanowires (Figure
1a), tetrapod structures (Figure 1b),
microtubes (Figure 1c), microspheres
Aurangzeb Khan: Raman Spectroscopic Study………
J Pak Mater Soc 2010; 4(1)
(Figure 1d), nanorods (Figure 1e) and
flower-like (Figure 1f). XRD (not shown
here) revealed that all the structures had
hexagonal wurtzite crystallographic
phase and the EDX (not shown either)
confirmed that there were no impurities
at the detection level. The growth
conditions and discussions can be found
elsewhere7.
The Raman-scattering spectra of the as-
grown ZnO structures are shown in
Figure 2 with 532 nm laser light
(Nd:YAG) laser as an excitation source.
The Raman signals are usually very
sensitive to the structure of crystal as
well as to the defects in the crystal
structure. The crystal structure of ZnO is
wurtzite (hexagonal) which belongs to
the C 6v4 space group having two formula
units per primitive cell with all the atoms
occupying the C3v sites. According to
Group theory, there are eight sets of
zone centre optical phonons, where A1
and E1 modes are polar which split into
transverse optical (A1T and E1T) and
longitudinal-optical (A1L and E1L)
phonons, while the E2 mode consists of
two modes of low- and high-frequency
phonons (E2L and E2H) which are
Raman-active12-13. The main dominant
sharp peak labeled as E2 at 437 cm-1
was observed and is known as Raman-
active optical phonon mode, which is the
characteristic of wurtzite hexagonal
phase ZnO. Other peaks are also
usually observed, i.e. the peak at ~98
cm-1 known as E2(Low), and the peak at
339 cm-1 is the second-order Raman
spectrum, originating from the zone-
boundary phonons 3E2H–E2L and the
peak at 388 cm-1 can be labeled as A1T.
The relatively higher intensity and sharp
peak of E2 mode at 437 cm-1 compared
to the other observed peaks,
demonstrated that the as-grown ZnO
6

Figure 1. SEM images of the as-synthesized ZnO nanostructures, a) nanowires, b)
spheres, c) nanorods, d) flower-like, e) tubular structures and f) tetrapods. The bar scale
are 10 µm, 2 µm, 3 µm, 20 µm, 10 µm and 1µm respectively.
structures are of wurtzite hexagonal
phase with good crystallinity.
Table 1 gives a comparison of the
Raman peak with the theoretical values
reported by Xu et. al4 and Khan A. et al6.
The comparison of the main E2(High)
peak is highlighted in red. The E2(High)
peak shifts are +4, +3, +8, +8, +9 and
+4 for the nanowires, spheres,
nanorods, flower-like, tubular and
tetrapods respectively. It is worth noting
that E2(High) is blue-shifted in all the
morphologies, the E2(Low) is red-shifted
for nanorods and sphere-like structures,
while E2(low) was not visible in other
structures. Similarly, the other relative
shifts are given in Table 1.
Table 2 gives a comparison of the
Raman modes between the above
mentioned ZnO nanostructures and the
bulk ZnO. The E2(High) mode is blue-
shifted by 5, 4, 6, 6, 7 and 5 for
nanowires, spheres, nanorods, flower-
like, tubular and tetrapods respectively.
Similarly, the other peaks and their
relative shifts are presented. The blue-
shift in E2(High) can be due to the
Aurangzeb Khan: Raman Spectroscopic Study………
J Pak Mater Soc 2010; 4(1)
optical phonon confinement by
nanostructures, laser Induce heating
and/or the phonon localization by
defects or impurities in the
nanostructures or due to anisotropic
internal strains corresponding to
different growth directions. The optical
phonon confinement is possible in our
case, as the nanostructures are bigger
in size than the Bohr exciton radius in
ZnO (2.3 nm). To investigate the laser
induced heating effect, we performed a
series of experiments with laser intensity
varying from 5 mW to 25 mW with the
same spot size (500 nm), and the same
shifts were observed, so this may not be
the case either. When nanostructures
are formed or synthesized, different
morphologies may have different growth
directions as well as internal strains, and
we suspect that these nanostructures
have defects as well (Photo-
luminescence study showed defect
levels, to be reported elsewhere) which
is why the E2(High) is blue-shifted.
7
 J Pak Mater Soc 2010; 4(1)

Figure 2. Raman spectra of various as-grown nanostructures. The main peak E2 (High)
shows blue shift for all nanostructures in comparison with the theoretical and
experimental bulk counter parts.
Table 1. A comparison of the Raman active modes of the various ZnO nanostructures
with the theoretical results. Peak position under each title along with the peak shift is
listed. All values are in cm-1.

Table 2. Raman spectra of ZnO nanostructures compared with the experimental bulk
ZnO. Note the peak positions under each title along with the shift (in cm-1).

Aurangzeb Khan: Raman Spectroscopic Study……… 8


Conclusion
In summary, we have studied the
Raman spectra of various morphologies
of ZnO such as nanowires, spheres,
nanorods, flower-like, tubular and
tetrapods. We found that the E2(High)
mode depends on the morphology of
nanostructures and shows blue-shift in
all morphologies when compared with
the theoretical and experimental results.
We believe that this blue-shift in
E2(High) is due to defects and internal
strains due to different growth directions.
This study may be very important in
understanding various morphologies of
ZnO and their corresponding growth.
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