Current Applied Physics 11 (2011) 93e97

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Current Applied Physics

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Observation of catalytic properties of CdSeZnO composite nanorods synthesized

by aqueous chemical growth technique
J. Nayak*, H. Lohani, T.K. Bera
Department of Physics & Meteorology, Indian Institute of Technology, Kharagpur-721302, West Bengal, India

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

Article history: We have synthesized the nanorods of CdSeZnO composite by chemical method and have investigated
Received 14 December 2009 their structure, optical and electrical properties by suitable techniques. The X-rays diffraction results
Received in revised form prove the co-existence of CdS and ZnO in usual hexagonal structure and no peak corresponding to any
22 June 2010
intermediate phase has been identified. The above observation has been confirmed by micro-Raman
Accepted 23 June 2010
study. The photo-current action spectra of CdSeZnO nanorods show a significant enhancement of the
Available online 27 June 2010
photo-current due to visible sensitization by surface CdS layer. In an attempt to explore the catalytic
activity of CdSeZnO, the photodegradation of 3,4-dihydroxy benzoic acid has been investigated under
Keywords:
Catalysis
visible irradiation from a halogen lamp. The concentration of aqueous solution of 3,4-dihydroxy benzoic
Composite acid decreases with increase in the irradiation time which is attributed to photodegradation of the
Raman-spectroscopy benzoic acid. A possible mechanism for the redox reactions responsible for degradation of the benzoic
Photo-current acid has been suggested.
Nanorod Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction
During recent decades, a great attention has been devoted
towards the utilization of semiconductor and metal nanoparticles
for catalysis [1]. Semiconductor nanoparticles have been success-
fully employed for catalytic degradation of various water pollutants
like phenol [2], methyl orange [3] and 3,4-dihydroxy benzoic acid
[4]. Semiconductors with wide band gaps are reported to exhibit
a higher efficiency of photocatalysis, for example, the photo-
catalytic activities of the nanoparticles of the TiO2 and ZnO are well
known [5e10]. However, because of wide band gap, they are active
only under ultraviolet irradiation. Since only 3% of the solar radi-
ation lies in the ultraviolet range, the efficiency of TiO2 and ZnO
based solar catalyst is supposed to be extremely low. In order to
enhance the catalytic efficiency, it is imperative to couple the above
wide band gap semiconductor with a lattice matched visible
sensitizer. CdS is considered to be the most suitable visible sensi-
tizer for ZnO because the lattice structure of CdS is same as that of
ZnO, the band gap of CdS lies in the visible range and the CdS forms
a type-II heterojunction with ZnO which facilitates a very fast, inter-
band charge transfer from CdS to ZnO. The lifetime of the photo-
generated carrier in CdSeZnO composite was observed to be higher
* Corresponding author.
E-mail address: nayak@phy.iitkgp.ernet.in (J. Nayak).
than that in the only ZnO and only CdS. The above process is
responsible for an enhanced efficiency of visible photocatalysis.
Although there are several articles about the UV photocatalysis of
ZnO [9,10], the visible photocatalysis of CdSeZnO has not yet been
published. In this report, we demonstrate a successful photo-
degradation of 3,4-dihydroxy benzoic acid in presence of CdSeZnO
composite nanorods as catalyst, under visible irradiation from
a 300 W halogen lamp.
2. Experimental
A two step procedure was followed in order to grow CdSeZnO
composite nanorods on conducting silicon substrates. Nþ-Si (100)
wafer was ultrasonically cleaned in acetone, ethanol and DI water
(r ¼ 18 Mu cm) and successively immersed in strong HF for
removal of the surface SiO2 layer. A polycrystalline buffer layer of
ZnO having a thickness of 2 mm, approximately, was deposited on
the Si wafer by dip coating in an isopropanolic solution of Zn

(CH3COO)2.$6H2O followed by annealing at 500 C in O2 atmo-
sphere for 30 min (for crystallization and oxidation). In order to
grow the nanorods of ZnO, the above samples were immersed in
a capped laboratory pyrex bottle containing equal volume of
aqueous solutions of 0.1 mM Zn(NO3)2 and 0.1 mM (CH2)6N4. Then,
the bottle was kept inside a regular laboratory oven and the

mixture was refluxed at 120 C for 24 h. After 24 h, the bottle was
cooled to room temperature, all the samples were taken out of the

1567-1739/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2010.06.025
94 J. Nayak et al. / Current Applied Physics 11 (2011) 93e97


solution, thoroughly rinsed in DI water and dried at 60 C for 6 h. In
order to deposit CdS on the ZnO nanorods, we followed the well
known chemical bath deposition technique [11]. The samples
containing nanorods of ZnO on Si/ZnO substrates were dipped in
alkaline aqueous solutions (pH ¼ 10, NH4OH) of Cd(CH3COO)2

(0.1 mM) and (NH2)2CS (0.2 mM) followed by drying at 80 C in
laboratory oven. During chemical bath deposition, the precursor

solutions were maintained at 60 C under continuous stirring. We
prepared three sets of samples with different deposition time,
20 min, 45 min and 1 h.
The SEM micrographs were recorded with a JEOL JSM 3010 field
emission SEM with resolution of 40 nm. The X-rays diffraction was
carried out with a Philips X’pert diffractometer in the low angle
configuration. The micro-Raman spectrum was recorded with JY
Raman spectrometer equipped with an argon laser, Ramanour
double monochromator (resolution, 1 cm1) and an LN2 cooled CCD
detector. The laser power was maintained at 5 mW in order to avoid
any thermal degradation of the sample. In order to measure the
photo-current, a photo-electrochemical cell was designed with
CdSeZnO/Nþ-Si as the cathode, platinum anode, saturated calomel Fig. 1. Scanning Electron Microscopic image of CdSeZnO composite nanorods grown
electrode as the reference electrode and a mixture of aqueous on Nþ Si (111) substrate by aqueous chemical growth method.
solutions of 1 M KCl and 0.1 M Na2S as the electrolyte. The light
source was a 300 W halogen lamp with spectral range from 420 nm
to 800 nm. The photodegradation of the 3,4-dihydroxy benzoic acid formation because of diffusion of Cd or S component from the
was studied under visible illumination from the same 300 W surface in to the ZnO lattice. The peaks from CdS have higher FWHMs
halogen lamp in presence of CdSeZnO composite nanorods as the compared to that from ZnO which indicates the presence of ultra
catalyst. The aqueous solution of the DHBA was treated separately small CdS nanoparticles. The intensity of CdS peak is expected to be
with ZnO nanorod assembled thin film and CdSeZnO composite higher than that from ZnO because CdS forms the top layer. The
nanorod assembled thin film. For the above purpose, 15 ml of dilute substrate being single crystalline does not contribute to the XRD
aqueous solutions of DHBA, with concentrations of 0.2 mg l1, were spectrum. The intensity of the XRD peak with respect to the back-
separately taken in each of the four 25 ml transparent, colorless ground is observed to be weak because of higher surface roughness
glass vials. In the first bottle, the CdSeZnO/Si sample was of the sample. The surface roughness of our sample is believed to be
immersed, in the second bottle the ZnO/Si was immersed, in the high because the CBD grown CdS could not form a continuous layer
third bottle CdS/Si was immersed and in the fourth bottle there was on ZnO nanorods [14]. Instead, there could be sparsely deposited

no catalyst. All four bottles were sealed, maintained at 30 C, ultra small nanocrystals of CdS attached to ZnO nanorods. At
uniformly illuminated with a 300 W halogen lamp and continu- present, the TEM experiment is in progress to find out the detailed
ously stirred with magnetic stirrers for 24 h. About 3 ml of solution lattice structure.
was periodically sampled out through the cork cap of each bottle In order to confirm the co-existence of crystalline CdS and ZnO,
for the UVeVIS absorption measurement with a Shimadzu UV-3100 we carried out micro-Raman spectroscopic study. Fig. 3 shows the
PC spectrophotometer. Raman spectra of the samples before and after CdS deposition. For
all Raman spectra, the background correction was performed with
3. Results and discussion the LABSPEC3 software supplied with the system. Before CdS
deposition, one sharp peak corresponding to E2 (LO) of hexagonal
Fig. 1 shows the SEM micrograph of CdSeZnO nanorods,
CdS (002)

randomly oriented but densely packed on conducting Si substrate.

The diameter of the nanorod is at least 100 nm and length is several
micron. The orientation of the nanorods could not be controlled
CdS (101)
CdS (100)

because of structural mismatch between cubic Si and hexagonal

ZnO. The buffer layer was not effective enough to provide nucle-
CdS (110)
ZnO (100)

ZnO (101)

ation centers for growth of aligned nanorods [12]. The shape of the
CdS (112)
Intensity (Arb. U)

tip of the nanorod depends on the rate of growth along different

ZnO (102)

crystallographic directions which is determined by the tempera-

ZnO (110)

ture of the reaction medium. Usually, hexagonal tips are formed at

higher temperature, however, we got a mixture of hexagonal and
sharp tipped nanorods because the temperature was moderately

high (120 C) [13].
Fig. 2 shows the low angle X-rays diffraction (XRD) spectrum of
CdSeZnO composite nanorods where one can observe a series of
peaks corresponding to hexagonal CdS and ZnO. XRD peaks corre-
sponding to the reflections from (100), (101), (102) and (110) planes
of hexagonal ZnO and that corresponding to the reflections from 20 30 40 50 60
(100), (002), (101), (110), (102) and (112) planes of hexagonal CdS are
2 (Deg.)
clearly observed in the spectrum. We did not observe any structural
transformation of either ZnO or CdS and neither did we observe any Fig. 2. Low angle X-rays diffraction spectrum of CdSeZnO composite nanorods
XRD peak corresponding to any intermediate compound (alloy) deposited on Nþ Si (111) substrate.
 J. Nayak et al. / Current Applied Physics 11 (2011) 93e97 95

a 0.055 CdS-ZnO (60 Min.)

-1 0.050 CdS-ZnO (45 Min.)
439 cm
0.045 CdS-ZnO (20 Min.)
0.040 ZnO/Si
0.035

IPCE (%)
Intensity (Arb. U.)

0.030

0.025

0.020

0.015

0.010

0.005

0.000
450 500 550 600 650 700
Wavelength (nm)
350 400 450 500

Wavenumber (cm )
-1 Fig. 4. Photo-current action spectra of CdSeZnO composite nanorods with different
thickness of chemically deposited CdS, the electrolyte is an aqueous solution mixture
of 1 M KCl and 0.1 M Na2S.
b CdS (1LO)
the excitation wavelength fall below 500 nm, a significant decrease
in IPCE (%) has been observed which could be attributed to two
possible reasons. (1) Saturation of absorption due to the large
absorption cross-section in the UV region compared to that in the
visible region leads to a lower effective IPCE (%). (2) The penetration
Intensity (Arb. U)

of the UV radiation suffers a lot due to scattering at lower wave-

length and significant absorption of UV by ITO substrate [18].
Looking at the photo-current spectra of three sets of samples, one
ZnO (E2(LO)) should notice that with increase in the deposition cycles of CdS, the
IPCE (%) increases. Since the source of excitation is halogen lamp
(visible radiation), the carrier generation is supposed to be from the
CdS only. Thicker is the CdS layer, higher is the concentration of the
photo-generated carriers and hence higher is the IPCE (%). The band
gap of the bulk CdS is 2.24 eV which corresponds to the wavelength
of 500 nm. The observed band gap is lower than the bulk value
200 250 300 350 400 450 500 because of the surface states that act as intermediate steps for
Wavelength (nm) conduction of the electrons. The above observation demonstrates
a successful generation of the electronehole pairs in the CdS and
Fig. 3. Micro-Raman spectrum from; (a) ZnO nanorods showing 1LO mode of hexag- consequent transfer of the electrons from the conduction band of
onal ZnO, (b) CdSeZnO composite nanorods showing 1LO mode of hexagonal CdS and
the CdS to the conduction band of the ZnO. The band diagram of the
1 LO mode of hexagonal ZnO.
CdSeZnO composite structure is shown in Fig. 5(a). The electron
ZnO is observed at 439 cm1 [15], whereas after CdS deposition, affinity of the CdS is higher than that of the ZnO. Therefore,
one can observe a couple of peaks at 301 cm1 and 438 cm1. The according to Anderson’s model, a type-II heterojunction is formed
peak at 301 cm1 corresponds to 1LO from hexagonal CdS [16]. The
peak exhibits an inhomogeneous broadening towards the lower
wave number region which evidences the presence of ultra small
CdS nanoparticles. The Raman spectrum from CdSeZnO composite
sample has lower signal to noise ratio compared to that from ZnO
because of increased surface roughness after CdS deposition.
The broad peak at 438 cm1 corresponds to E2 (LO) of hexagonal
ZnO. Due to deposition of CdS, the Raman intensity from ZnO
decreases with increase in the FWHM. The reduction of intensity is
expected because of scattering in the CdS nanocrystals attached to
the ZnO nanorod. However, the red shift and the inhomogeneity are
not yet well understood. Since the diameter of the nanorod is at
least 100 nm, there can be no phonon confinement effect. The only
reason for the red shift and the inhomogeneity in the peak could be
a lattice strain at CdS/ZnO interface [17].
Fig. 4 shows the photo-current action spectrum of ZnO and
CdSeZnO nanorod. The spectrum of ZnO is completely flat in the
visible region because the band gap of ZnO corresponds to 367 nm.
Fig. 5. (a) A proposed band diagram for CdSeZnO composite structure showing
On the other hand, the CdSeZnO composite nanorods start transfer of the photo-generated electrons from the conduction band of CdS to the
responding at 550 nm as indicated by a sharp increase in the IPCE conduction band of ZnO. (b) Schematic of the surfaces of CdS and ZnO showing the
(%) with decrease in the wavelength of excitation. However, when surface adsorbed ions.
96 J. Nayak et al. / Current Applied Physics 11 (2011) 93e97
between the CdS and the ZnO. The visible radiation from the
halogen lamp generates electronehole pairs in the CdS. The elec-
trons from the conduction band of the CdS are quickly transferred
to the conduction band of the ZnO. The time required for the
transfer of the electron is about 18 ps [19,20] which is smaller than
the electron’s lifetime in the CdS. Once the electrons diffuse into the
conduction band of the ZnO, the probability of their decay is small
because there can be no free hole in the ZnO under visible excita-
tion. As a result, the electrons accumulate in the conduction band of
the ZnO and the holes accumulate in the valance band of the CdS. In
this way, the charge separation is achieved. The above charge
transfer process can be summarized in following manner.



CdSðhnÞ/CdS e þ  þ
cb /hvb /CdS et þ ht



CdS e
t þ ZnO/CdS þ ZnO e
cb
h i
ðCdSÞn þhþ 2þ 
t / ðCdSÞn1 Cd Ssurf
where e þ
cb and hvb stand for the electron in the conduction band and
the hole in the valance band respectively. Again, e þ
t and ht are the
electrons and the holes, respectively, trapped on the surface of the
nanorod/nanocrystal. As shown in Eq. (3) S ions accumulate on
the surface of CdS and retain their charge up to a characteristics
lifetime of 109 s, before being oxidized by surface adsorbed
organic molecules. Similarly, the electrons in the conduction band
of ZnO diffuse on to the surface of the nanorod and ionize the
chemisorbed oxygen molecules from the atmosphere. As a result,
O2 ions accumulate on the surface of the ZnO nanorod (as shown in
Fig. 5(b)). These O 2 ions act as an efficient reducing agent for
surface adsorbed organic molecules. Here, we would like to
mention that the CdS layer is thinner than the room temperature
diffusion length of the electrons. Therefore, the charge transfer
from the CdS into the ZnO could be considered to be a ballistic
process. The CdS layer is discontinuous and too thin to support an
interfacial depletion layer. Therefore, the macroscopic potential
barrier does not exist at the CdS/ZnO interface. The diffusion of the
photo-generated electrons from the CdS into the ZnO, a wide band
gap semiconductor, helps the charge separation and suppresses the
recombination. As a result, the lifetime of the photo-generated
electron increases. When the lifetime exceeds the time it would
take to diffuse on to the surface of the nanorods, the efficiency of
the catalytic reduction of the surface adsorbed molecules is
significantly enhanced.
In order to investigate the photocatalytic activity of CdSeZnO,
we have chosen 3,4-dihydroxy benzoic acid as the precursor
because it is a common water pollutant present in the sewage from
the olive oil industry. Fig. 6 shows the UVeVIS absorption spectra of
aqueous solution of DHBA treated with CdSeZnO/Si where one can
notice three characteristic peaks at 200 nm, 250 nm and 293 nm
with a shoulder at 216 nm [21]. Due to treatment with CdSeZnO in
presence of visible radiation from the halogen lamp, the concen-
tration of the solution starts decreasing after at least 12 h, as
indicated by a decrease in the intensities of all three peaks. Since
neither we applied any bias nor used any scavenger, the catalytic
degradation is believed to be due to both oxidation and reduction
reactions attributed to the holes in the CdS and the electrons in the
ZnO respectively. The detail mechanism of the chemical reaction is
still unknown. The surface adsorbed O 2 ions on the ZnO surface and
the S ions on the CdS surface are responsible for the reduction and
oxidation respectively of DHBA molecules. The rate of catalytic
degradation is expected to be high because both the charge carriers
participate in the redox reactions. However, in this case, the
degradation starts only after 12 h showing a lower efficiency of the
3.0
2.5 Fresh Solution
2.0
Absorbance
1.5
1.0
12 hrs
0.5 15 hrs
18 hrs
(1) 0.0 24 hrs
(2) 150 200 250 300 350
Wavelength (nm)
(3) Fig. 6. UVeVIS absorption spectra of aqueous solution of 3,4-dihydroxy benzoic acid
after treatment with CdSeZnO catalyst in presence of visible radiation from a halogen
lamp.
process. The lower intensity of the halogen lamp (i.e. 300 W) could
be responsible for such a lower efficiency. At present, the experi-
ments are in progress with an aim to improve the efficiency of the
catalysis. The results will be communicated in near future. Here we
would like to mention that the concentration of the solutions of
DHBA treated with only CdS, only ZnO and no catalyst did not
change at all even after 24 h.
4. Conclusion
We have successfully grown the nanorods of CdSeZnO on con-
ducting silicon substrate by aqueous chemical growth. The nano-
rods are randomly oriented on the substrate because of lattice
mismatch. The Raman spectrum contained the longitudinal optical
phonon peaks from hexagonal CdS as well as ZnO. 3,4-dihydroxy
benzoic acid could be photodegraded in the presence of CdSeZnO
as the catalyst, under visible irradiation.
Acknowledgment
We gratefully acknowledge Prof. A.K. Thakur, Department of
Physics, IIT Kharagpur for providing substantial help in sample
preparation and constant encouragement. Prof. S.N. Sahu, Institute
of Physics, Bhubaneswar, India is acknowledged for help in Raman
spectroscopy study.
References
[1] Alexis T. Bell, Science 299 (2003) 1688e1691.
[2] A. Sclafani, L. Palmisano, G. Marci, A.M. Venzia, Solar Energy Material & Solar
Cells 51 (1998) 203e219.
[3] G.T. Brown, J.R. Darwent, J. Phys. Chem. 88 (1984) 4955e4959.
[4] I. Poulios, D. Makri, X. Prohaska, Glob. Nest Int. J. 1 (1999) 55e64.
[5] Dung Duonghang, Jermy Ramsden, Michael Gratzel, J. Am. Chem. Soc. 104
(1982) 2977e2985.
[6] R. Rossetti, L. Brus, J. Phys. Chem. 86 (1982) 4470e4472.
[7] J. Moser, M. Gratzel, J. Am. Chem. Soc. 105 (1983) 6547e6555.
[8] M.A. Fox, B. Lindig, C.C. Chen, J. Am. Chem. Soc. 104 (1982) 5828e5829.
[9] J. Liqiang, W. Baiqi, X. Baifu, Li Shudan, S. Keying, C. Weimin, Fu Honggang,
J. Sol. State Chem. 177 (2004) 4221e4227.
[10] C. Hariharan, Appl. Catal. A 304 (2006) 55e61.
[11] Isaiah O. Oladeji, Lee Chow, J. Electrochem. Soc. 144 (1997) 2342e2346.
[12] L. Vayssieres, Int. J. Nanotechnology 1 (2004) 1e41.
[13] Q.L. Hong, S.J. Chua, K.P. Loh, C. Zhen, C.V. Thompson, E. Fitzgerald, Appl. Phys.
Lett. 87 (2005) 101908 [3 pages].
[14] W.Q. Han, A. Zettl, Appl. Phys. Lett. 81 (2002) 5051e5053.
 J. Nayak et al. / Current Applied Physics 11 (2011) 93e97 97

[15] J. Jie, G. Wang, Y. Chen, X. Han, Q. Wang, B. Xu, J.G. Hou, Appl. Phys. Lett. 86
(2005) 031909 (3-pages).
[16] P. Nandakumar, C. Vijayan, M. Rajalakshmi, A.K. Arora, Y.V.G.S. Murti, Physica
E 11 (2001) 377e383.
[17] J.N. Zeng, J.K. Low, Z.M. Ren, T. Liew, Y.F. Lu, Appl. Surf. Scince 197-198 (2002)
362e367.
[18] G. Wang, X. Yang, F. Qian, J.Z. Zhang, Y. Li, Nanoletters 10 (2010) 1088e1092.
[19] K.R. Gopidas, M. Bohorquez, P.V. Kamat, J. Phys. Chem. 94 (1990)
6435e6440.
[20] S. Hotchandani, P.V. Kamat, J. Phys. Chem. 96 (1992) 6834e6839.
[21] E. Andre, J.P. Cornard, C. Lapouge, Chem. Phys. Lett. 434 (2007)
155e159.