Graphene oxide based hybrid nanostructures with ZnO thin films and nanorods

,
R. Nandi , V. Divakar Botcha, Gulbagh Singh, Wasi Uddin, Devendra Singh, S. S. Talwar, R. S. Srinivasa, and S.
S. Major

Citation: AIP Conference Proceedings 1665, 080027 (2015); doi: 10.1063/1.4917931

View online: http://dx.doi.org/10.1063/1.4917931
View Table of Contents: http://aip.scitation.org/toc/apc/1665/1
Published by the American Institute of Physics
 Graphene Oxide based Hybrid Nanostructures with ZnO
Thin Films and Nanorods
R. Nandi1,*, V. Divakar Botcha1, Gulbagh Singh1, Wasi Uddin4, Devendra Singh3,
S. S. Talwar1, R. S. Srinivasa2 and S. S. Major1
1
Department of Physics, Indian Institute of Technology Bombay, Mumbai – 400076, India
2
Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai
– 400076, India
3
Centre for Research in Nanotechnology and Science, Indian Institute of Technology Bombay, Mumbai – 400076,
India
4
Centre for Nanoscience and Nanotechnology, Jamia Millia Islamia, New Delhi – 110025, India
*E-mail: rajunandi@iitb.ac.in

Abstract. Graphene oxide (GO) monolayer sheets were transferred on to sputtered ZnO films and chemically grown
ZnO nanorods by Langmuir-Blodgett technique. SEM images show that the GO sheets are well defined and uniformly
distributed over both surfaces, namely, ZnO film and ZnO nanorods. Raman studies show that the ZnO film has a higher
reducing effect on GO monolayers compared to ZnO nanorods, with the most effective reduction at intermediate
temperatures in the range of 400 - 600 oC, and a degradation of GO sheets on both structures, after heat treatment at 800
o
C. Photoluminescence spectra of heat treated GO/ZnO film and GO/ZnO nanorods show characteristic near-band-edge
emission of ZnO, which is not significantly affected by the presence of RGO sheets.
Keywords: Graphene oxide, Langmuir-Blodgett, ZnO, nanorods, sputtering, chemical bath deposition
PACS: 68.18.g, 81.15.Cd, 61.46.Km, 78.67.Qa

INTRODUCTION Raman spectroscopy and photoluminescence (PL)

Graphene/ZnO hybrid nanostructures are currently
attracting attention for a wide range of potential
applications in photovoltaics, optoelectronics and
photocatalysis [1]. Reduced graphene oxide (RGO) is
the de-oxygenated form of graphene oxide (GO), which
is considered to be a low cost and scalable alternative to
graphene for various device applications. RGO is also
being used to form hybrid nanostructures with ZnO by
solution based process of GO and ZnO, followed by
suitable reduction treatments and it has been indicated
that the presence of ZnO in GO/ZnO nanocomposites
has a reducing effect on GO [2]. The present work
attempts to explore and substantiate the interaction
between GO and ZnO, in GO/ZnO hybrid
nanostructures, using both ZnO thin films as well as
nanorods. GO monolayer sheets have been transferred
in this work by Langmuir-Blodgett (LB) technique on
to rf sputtered ZnO thin films and chemically grown
ZnO nanorods. The effect of LB transfer conditions on
the morphology of the hybrid nanostructures was
studied by scanning electron microscopy (SEM).
spectroscopy were employed to understand the reducing
effect of ZnO on GO sheets and explore the effect of
RGO sheets on the PL of ZnO thin films and nanorods.
EXPERIMENTAL DETAILS
ZnO thin films of thickness ~200 nm were deposited
by reactive rf sputtering of zinc target at room
temperature (RT) in 20 % oxygen ambient. ZnO
nanorods were grown on the ZnO films as seed layers,
by chemical bath deposition through the reaction of zinc
nitrate (0.05 M) and hexamethylenetetramine (0.125 M)
at 95 °C for 8 hrs. GO synthesized by modified
Hummers-Offeman's method and dispersed in
methanol:water (1:5) was spread at the air-water
interface and transferred by LB technique on to the
sputtered ZnO films as well as on the ZnO nanorods,
using a KSV 3000 instrument. LB deposition was
carried out under optimized subphase pH and GO
concentration [3]. The sheets were transferred at a
lifting speed of 3 mm/min and barrier speed of 5
mm/min, but the target pressure was varied to optimize

Solid State Physics

AIP Conf. Proc. 1665, 080027-1–080027-3; doi: 10.1063/1.4917931
© 2015 AIP Publishing LLC 978-0-7354-1310-8/$30.00

080027-1
the morphology of GO sheets. After deposition, the
hybrid structures were heat treated for 1 hour in vacuum
at different temperatures in the range of 200-800 °C.
Morphological studies were carried out by a JEOL
model JSM-7600F FESEM. A Horiba Jobin Yvon HR
800 confocal Raman microscope equipped with a 514
nm Ar+ laser was used for Raman studies. Room
temperature PL measurements were carried out using
He-Cd laser (λ = 325 nm) and a Jobin-Yvon-Spex HR
460 grating monochromator.
RESULTS AND DISCUSSION
target pressures above 20 mN/m (images not shown).
The GO sheets transferred at 10 mN/m were thus
chosen for heat treatment and further characterization.
The corresponding GO/ZnO film and GO/ZnO nanorod
hybrid structures did not exhibit any morphological
changes on heat treatment up to 600 °C. However, after
heat treatment at 800 °C, the images of both the
structures show low contrast images of GO sheets,
indicating reduction in thickness, possibly due to
thermal degradation.
(a) (b)
ZnO film ZnO
Nanorod

Fig. 1 shows a typical surface pressure – area

isotherm for GO sheets at the air-water interface. The 200 nm 200 nm
sheets exhibit gas phase behavior at large areas, but on
GO/ZnO film GO/ZnO Nanorod
compression, an increase in surface pressure is (1 mN/m)
(1 mN/m)
observed below certain area, below which, the isotherm
exhibits a nearly constant slope, liquid – condensed
region with a sharp increase in surface pressure.
12

20 20
Surface Pressure (mN/m)

10

8
µm µm
GO/ZnO film GO/ZnO Nanorod
6 (10 mN/m) (10 mN/m)
4

200 400
2
600 800 20 20
Area (cm )
µm µm
FIGURE 1. Typical surface pressure – area isotherms of
GO sheets at the air-water interface. FIGURE 2. SEM images (a) ZnO film and GO/ZnO film
structures (transferred at target pressures, as indicated) and (b)
The SEM image of ZnO thin film is shown in Fig. ZnO nanorods and GO/ZnO nanorods (transferred at target
2(a) along with the images of GO sheets transferred pressures, as indicated).
over it at target pressures of 1 mN/m and 10 mN/m, as (a) (b)
indicated. Similarly, Fig. 2(b) shows the SEM image of
the top surface of ZnO nanorods along with the images
of GO sheets transferred over it at target pressures of 1
mN/m and 10 mN/m. The image of the ZnO film shows
uniform and compact surface features with lateral size 20 µm 20 µm
in the range, 60-80 nm. On the other hand, the ZnO
nanorods exhibit a relatively low surface density with FIGURE 3. SEM images of (a) GO/ZnO film and (b)
an average diameter of ~200 nm (their lengths being ~ GO/ZnO nanorods after heat treatment in vacuum at 800 °C.
3 µm, as seen from cross sectional image, not shown).
Fig. 4 (a) and (b) show the Raman spectra of the
It is also seen that on both substrates, patchy and non-
as-transferred and heat treated GO/ZnO film and
uniformly distributed GO sheets of low surface density
GO/ZnO nanorod structures, respectively. Intense, D
are transferred at a target pressure of 1 mN/m, which
and G Raman peaks of GO at 1345±2 cm-1 and 1596±2
corresponds to the lower end of the liquid condensed
cm-1, respectively, are clearly seen for both structures,
region of the isotherm, where the monolayer at the air-
in the as-transferred condition, as well as after heat
water interface is more compressible. In contrast,
treatment at up to 600 °C. The absence/loss of intensity
closely spaced and uniformly distributed GO sheets are
of Raman peaks after heat treatment at 800 °C is
transferred on both substrates at a higher target pressure
attributed to the possible degradation of GO/ZnO
of 10 mN/m. The surface density of GO sheets tends to
structures, owing to the sintering and grain growth of
increase further with increase of target pressure, and
ZnO surface at higher temperatures. A noticeable
GO sheets with substantial overlap are transferred at
recrystallization of the ZnO film surface was observed

080027-2
by SEM (not shown) and more detailed investigations temperature and compared with the corresponding
are in progress for both structures. The Raman spectra of ZnO film and ZnO nanorods (without GO
spectrum of GO/ZnO film shows no changes after heat sheets), after being subjected to similar heat treatments
treatment at 200 °C, but heat treatment at 400 °C (400 oC and 600 oC, respectively). These results are
results in a large red shift of the G-peak to 1586 cm-1, a shown in Fig. 5. All the samples exhibit UV emission
value close to that of graphene, indicating a substantial peak at ~378 nm, due to the near-band-edge emission
reduction of GO and recovery of the graphitic network. and a weak and broad, longer wavelength defect
Interestingly, the Raman spectra of GO/ZnO film do emission is seen in the case of ZnO nanorods. It is
not exhibit any significant changes after heat treatment however, observed that the PL spectra of GO/ZnO
at 600 °C, indicating the absence of reduction effect. structure and the ZnO film after heat treatment at 400
Along similar lines, Fig. 4(b) shows the Raman spectra °C, exhibit nearly similar features and the same
of the GO/ZnO nanorods remain practically unchanged observation is true for the GO/ZnO nanorods and ZnO
for heat treatment up to 200 °C. After heat treatment at nanorods, after heat treatment at 600 oC. These results
400 oC, this structure exhibits a small red shift of G suggest the absence of any noticeable effect due to the
peak to 1598 cm-1, and a further red shift to 1595 cm-1, plasmonic effects of reduced GO in contact with ZnO
after heat treatment at 600 °C, indicating a much thin film or nanorods, in contrary to some recent
smaller extent of reduction in this case compared to the observations on RGO/ZnO nanostructures [4].
GO/ZnO film structure. The reducing effect of ZnO on 160
(a) (b)

GO is attributed to the presence of oxygen deficiencies 120

ZnO film 3000
ZnO nanorods

in ZnO. The limited reduction and the higher 80

2000

temperature requirement for reduction, observed in the 1000

Intensity (a.u)
40

Intensity (a.u)
case of GO/ZnO nanorods, compared to GO/ZnO film 0
0
are attributed to the lack of intimate surface contact and 160
GO/ZnO film GO/ZnO nanorods
decrease in contact area between GO and ZnO in the 120 2000

case of ZnO nanorods. The most effective reduction of 80

1000

GO/ZnO film at an intermediate temperature of 400 oC 40

0

is explained as follows. While the kinetics limit the 0

400 500 600 700 400 500 600 700
Wavelength (nm) Wavelength (nm)
reduction at temperatures below 400 °C, a possible
crossover of Ellingham curves (oxygen potential FIGURE 5. PL spectra of (a) GO/ZnO and ZnO film after
variation with temperature) of GO/RGO and Zn/ZnO at heat treatment at 400 °C and (b) GO/ZnO and ZnO
a temperature between 400 °C and 600 °C may be nanorods after heat treatment at 600 °C.
responsible for the lack of reduction at higher In summary, uniformly distributed, well defined
temperatures. and adherent GO monolayer sheets were transferred on
(a) (b) to sputtered ZnO film and ZnO nanorods by LB
As 1345 1596 As 1345 1602 technique. Raman studies show that the ZnO thin film
transferred transferred
surface has a higher reducing effect on GO monolayers
1345 1596 1344
1601 compared to ZnO nanorods surface, particularly when
200 °C
200 °C heat treated at 400 °C. Heat treatment of both GO/ZnO
1586 1346 1598 hybrid structures at 800 oC results in degradation of GO
Intensity (a.u.)

Intensity (a.u)

1365
400 °C 400 °C sheets. The presence of RGO sheets do not result in
1595
1596
1348 enhancement of PL from ZnO.
1353
600 °C
600 °C

800 °C
ACKNOLEDGEMENTS
800 °C 1350 1602 SAIF, IIT Bombay is acknowledged for SEM and
Raman measurements.
1200 1400 1600 1200 1400 1600
REFERENCES
Wavenumber (cm- Wavenumber (cm- 1. W. I. Park, C. H. Lee, J. M. Lee, N. J. Kim, G. C. Yi,
FIGURE 4. Raman spectra (a) GO/ZnO film and Nanoscale, 3 3522-3533 (2011).
(b) GO/ZnO nanorods in the as-transferred 2. B. J. Kwon, J. Kim, S. Choi, S. J. An , Nanotechnology
condition and after heat treated at temperatures, as
25 085701-085708 (2014).
indicated.
3. V. D. Botcha, P. K. Narayanam, G. Singh, S. S. Talwar,
The above observations indicate a significant role of
R. S. Srinivasa, S. S. Major, Colloids Surf., A. 452 65-72
ZnO in the reduction of GO at ~ 400 °C in the case of
(2014).
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GO/ZnO nanorod structure. The photoluminescence 4. F. Han, S. Yang, W. Jing, K. Jiang, Z. Jiang, H. Liu, L.
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