Effect of cobalt doping on structural and optical properties of ZnO nanoparticles

,
J. Singh, A. Chanda , S. Gupta, P. Shukla, and V. Chandra

Citation: AIP Conference Proceedings 1731, 050091 (2016); doi: 10.1063/1.4947745

View online: http://dx.doi.org/10.1063/1.4947745
View Table of Contents: http://aip.scitation.org/toc/apc/1731/1
Published by the American Institute of Physics
 Effect of Cobalt Doping on Structural and Optical
Properties of ZnO Nanoparticles
J. Singha, A. Chanda*a, S. Guptaa, P. Shuklaa, V. Chandrab

a
Department of Physics, Dr. Harisingh Gour University, Sagar, M.P-470003, India
b
Department of Chemistry, Dr. Harisingh Gour University, Sagar, M.P-470003, India
* Email:anupamamatsc@gmail.com(Email of corresponding author)

Abstract Cobalt doped ZnO nanoparticles of uniform sizes were prepared by a chemical method using ZnCl 2 and NaOH as the
source materials. The formation of Co-doped ZnO nanoparticles was confirmed by transmission electron microscopy (TEM),
high resolution TEM (HR-TEM) and selected area electron diffraction (SAED) studies. The optical properties of obtained
products were examined using room temperature UV-visible and FTIR spectroscopy. SAED of cobalt doped ZnO nanoparticles
shows homogeneous distribution of nanoparticles with hexagonal structure. The HRTEM image of the Co-doped ZnO
nanoparticles reveals a clear lattice spacing of 0.52 nm corresponding to the interplanar spacing of wurtzite ZnO (002) plane.
The absorption band at 857 cm-1 in FTIR spectra confirmed the tetrahedral coordination of Zn and a shift of absorption peak to
shorter wavelength region and decrease in absorbance with Co doping.is observed in UV-Visible spectra.

Keywords: Nanoparticles, Wurtzite, HRTEM, ZnO

PACS: 78.67.Bf, 61.46.Df, 68.37.Og

INTRODUCTION
Zinc Oxide (ZnO), a wide and direct band gap (3.37
eV) semiconductor, has attracted much attention due to
its potential for various applications in optoelectronic,
sensor and piezoelectric fields [1-2]. By reducing the
size of ZnO crystals to nanoscale dimension,
researchers have been trying to tailor the optical,
electrical, magnetic and catalytic properties through
quantum confinement and surface effects. Along with
the advantages of nanoscale dimensionality
incorporation of dopants have offered new
functionality with changed properties. Several methods
have been approached for the synthesis of ZnO
nanoparticles, such as chemical or physical method
[3,4], hydrothermal process [5], sol−gel method [6],
and coprecipitation method [7]. Among these synthetic
routes, the chemical method has been popularly chosen
due to its simple and easy way of preparation, low
cost, uniformity and high yield of nanoparticles. In the
present work, pure and Co-doped ZnO NPs were
synthesized by the chemical method. Their structural
and optical properties were studied and magnetic study
is undertaken.
Experimental
The cobalt doped ZnO nanoparticles were prepared by
wet chemical method using zinc chloride (ZnCl2) and
sodium hydroxide (NaOH) and CoCl2 as the starting
materials. NaOH solution (dissolved in 50 ml distilled
water) was added drop by drop to soluble zinc chloride
(dissolved in 50ml of distilled water) under constant
stirring by magnetic stirrer to which CoCl2 was added
in proper ratio (10 wt% Co). The reaction was allowed
to proceed for 2h at room temperature, after complete
addition of CoCl2 and NaOH into the solution of ZnCl2
the solid and the solution phases were separated by the
centrifugation process and then the solid was washed
with distilled water several times to make that free of
salt and at the end with ethanol to absorb all the water
molecules present in that solid solution. White colored
solid was dried at 80 OC for 24h and then grinded for
the uniformities of the powder (nanoparticles).
Structural analysis of the synthesized samples was
carried out by high resolution TEM (EFI-Tecnai G2
F30 S-Twin) and optical study was done by UV-
Visible and FTIR spectroscopy (Bruker 37 Tensor).

DAE Solid State Physics Symposium 2015

AIP Conf. Proc. 1731, 050091-1–050091-3; doi: 10.1063/1.4947745
Published by AIP Publishing. 978-0-7354-1378-8/$30.00

050091-1
Results and Discussion
The absorption band at 857 cm-1 in FTIR spectra (Fig
2) confirms the tetrahedral coordination of Zn [8]. UV-
TEM image of 10 wt% Co-doped ZnO nanoparticles
Visible spectra (Fig.3) shows a shift of the absorption
displayed in Fig.1a shows hexagonal type structure
peak to shorter wavelength region and a decrease in.
along with agglomeration of number of particles.
absorbance in visible region in Co doped ZnO
Fig.1b shows the corresponding SAED pattern of Co-
nanoparticles.
doped ZnOnanoparticles which indicates
homogeneous distribution of nanoparticles. The
HRTEM image (Fig.1c) of the Co-doped ZnO
(a) ZnO
nanoparticles reveals a clear lattice spacing of 0.52 nm (b) 10% Co doped ZnO
1.2
corresponding to the interplanar spacing of wurtzite
ZnO (002) plane. 1.0
a

Transmittance
0.8

0.6

0.4

0.2
b
0.0
0 500 1000 1500 2000 2500 3000 3500
Wave number (cm-1)

FIGURE 2. FTIR spectra of (a) ZnO,

(b) 10% Co-doped ZnO nanoparticles
FIGURE 1a. TEM image of 10 % Co-doped
ZnO nanoparticles
The blue shift in absorption peak in Co-doped ZnO
nanoparticles is probably due to size effects (smaller
ionic radius of Co compared to ionic radius of Zn).
Also blue shift in absorption peak indicates increase in
bandgap which may be to Burnstein–Moss effect
Ozerov et al [9] reported a blue-shift in the bandgap in
nanocrystalline films. Yoo et al [10] observed a blue
shift in Al- and Co-codoped ZnO films which was.
attributed to the Burnstein–Moss effect from an
increase in the carrier concentration. Further analysis-
in this regard is undertaken. Decrease in absorbance in
Co doped ZnO nanoparticle may be due to Co
incorporation in ZnO lattice in substitutional site rather
than in interstitial sites creating defects.
FIGURE 1b. SAED pattern of 10% Co-doped
ZnO nanoparticles

0.9 (a) ZnO

(b) 10% Co doped ZnO
0.8

0.7

0.6
Absorbance

0.5 a
0.4

0.3

0.2
b
0.1

200 300 400 500 600

Wavelength (nm)

FIGURE 1c. HRTEM image of the 10% Co-

doped ZnO nanoparticles FIGURE 3. UV-Visible spectra of (a) ZnO(b)
10% Co-doped ZnO nanoparticles

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Conclusion
Co-doped ZnO NPs were successfully prepared by a
chemical method. TEM studies confirm the growth of
ZnO nanoparticles with some agglomeration. The
hexagonal (wurtzite) crystalline structure was
identified for Co-doped ZnO through HRTEM and
SAED analysis and FTIR spectra confirmed the
tetrahedral coordination of Zn. A shift of absorption
peak to short wavelength region and decrease in
absorbance with Co doping was observed in UV-
Visible spectra.

ACKNOWLEDGMENTS
The authors (A.Chanda, J.Singh, P. Shukla) wish to
acknowledge UGC for providing start-up grant to start
the research after joining in a Central University.

REFERENCES
1. Z.L.Wang, J.Phys:Condens. Matter 16, R829
(2004)
2. J.F.Wager, Science 300, 1245 (2003)
3. I. Djerdj, G. Garnweitner, D. Arcon, M. Pregeli,
Z. Jaqlicic, M. Niedegrberger, J. Mater. Chem.18,
5208−5217 (2008).
4. Z.R. Dai, Z.W. Pan and Z.L. Wang, Adv. Funct.
Mater, 13, 9 (2003).
5. L. Zhang, X. Liu, C. Geng, H. Fang, Z. Lian, X.
Wang, D. Shen, Q. Yan, Inorg. Chem. 52,
10167−10175 (2013).
6. S. Chakraborti, S. Sarwar, P. Chakrabarti, J. Phys.
Chem. B, 117, 13397−13408 (2013).
7. S. Zhang, F. Hu, J. He, W. Cheng, Q. Liu, Y.
Jiang, Z. Pan, W. Yan, Z. Sun, S. Wei, J. Phys.
Chem.C 117, 24913−24919 (2013).
8. K. Ravichandrika, P. Kiranmayi, R.V.S.S.N.
Ravikumar, International Journal of Pharmacy and
Pharmaceutical Sciences, 4, 336-338 (2012).
9. Ozerov, F. Chabre and W. Marine, Mater. Sci.
Eng. C 25, 614-617 (2005).
10. Y. Yoo, T. Fukumura, Z.Jin, K. Hasegawa,
M.Kawasaki, P. Ahmet, T. Chikyow and H.
Koinuma, J. Appl. Phys. 90, 4246-4250 (2001).

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