Characterization of Mechanically Activated ZnO Powders

by Raman, Luminescence and IR Spectroscopy

M. J. Scepanovic, Z. D. Dohcevic-Mitrovic, T. Sreckovic*, K. Vojisavljevic*, and
Z. V. Popovic

Center for Solid state Physics and New Materials, Institute of Physics, Belgrade, Serbia
*Center for Multidisciplinary Studies of the Belgrade University, Belgrade, Serbia

Abstract. Commercial zinc oxide powder was mechanically treated by grinding in a high-energy vibro-mill in a
continual regime in air up to 300 minutes. Original and modified ZnO samples were characterized by Raman,
photoluminescence (PL) and infrared (IR) spectroscopy. This study confirms that change in defect structure of ZnO
crystal lattice introduced by mechanical activation greatly affects the optical properties of this material.
Keywords: ZnO powder, Raman, luminescence, IR spectroscopy
PACS: 78.30.Am, Fs, 78.55.-m

Commercial zinc oxide powder (Kemika, p.a.
99.96 %) - ZnO(0), was mechanically activated by
grinding in a vibro-mill with steel rings (type MN
954/3, KHD Humboldt Wedag AG) in continual
regime in air (steel vessel volume 500 cm2, and
quantity of grinding powders 200 g). Grinding time
was 30 min for activated powder designated by
ZnO(30) and 300 min for ZnO(300). Average grain
size and microstrain value obtained from XRD are:
190 nm and -0.04 % for ZnO(0), 106 nm and -0.32 %
for ZnO(30), 44 nm and -0.78 % for ZnO(300) [1].
Raman measurements were performed at room
temperature in the backscattering geometry using
442 nm line of HeCd laser, Jobin-Yvon U1000
monochromator and photomultiplier as a detector.
Raman modes of the original sample can be assigned
to the Raman spectra of the bulk ZnO [2]. In the
Raman spectra of activated ZnO powders the intensity
of all observed modes decreases and their lineshape
become asymmetric, while i?2hlsh and i?i(LO) modes
shift to lower wave number with increasing activation
time. These changes originate from tensile strain
effects introduced by mechanical activation rather then
from the effects of phonon confinement because of
relatively great size of nanoparticles.
The photoluminescence (PL) spectra of original
and modified samples were excited by 325 and 442 nm
lines of a HeCd laser. It is observed that PL band in
yellow range in PL spectra excited by visible light
increases and shifts to lower wavelength as a
consequence of mechanical activation. On the
contrary, PL excited by UV light drastically decreases
with increasing activation time, as well as the ratio of
the green and yellow mode intensity. These results
suggest that oxygen vacancy complexes as well as
oxygen and Zn interstitials become dominant defects
in activated ZnO powders instead of isolated oxygen
vacancies in non-activated powder.
Far infrared (IR) reflectivity spectra were collected
by BOMEM DA8 spectrometer in the range between
50 and 650 cm"1, at room temperature. Differences
between IR spectra of original and activated samples
point out to the changes in the powder micro structure.
Besides A\ and E\ infrared active modes characteristic
for ZnO, a new IR band at -380 cm"1 appears in the
spectrum of ZnO(300), indicating the presence of a
small amount of iron-oxides due to long time grinding
in a vibro-mill with steel rings .
ACKNOWLEDGMENTS
This work was supported by the Serbian MSEP
under the projects No. 141047 and 14204OB.
REFERENCES
1. M. Scepanovic, T. Sreckovic, K. Vojisavljevic, M. M.
Ristic,S«. Sintering 38, 169 (2006).
2. C. A. Arguello, D. L. Rousseau, S. P. S. Porto, Phys.
Rev. 181,1351 (1969).
3. Y. Du, M.-S. Zhang, J. Hong, Y. Shen, Q. Chen, Z. Yin,
Appl. Phys. A 76, 171 (2003)

CP899, Sixth International Conference of the Balkan Physical Union, edited by S. A. Cetin and I. Hikmet
© 2007 American Institute of Physics 978-0-7354-0404-5/07/$23.00

648