Materials Research Bulletin 66 (2015) 7682

Contents lists available at ScienceDirect

Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

Structural, magnetic and electronic structure properties of Co doped

ZnO nanoparticles
Shalendra Kumar a,b, * , T.K. Song b, * , Sanjeev Gautam c, K.H. Chae c , S.S. Kim a , K.W. Jang a
a
b
c

Institute of Basic Sciences, Changwon National University, Changwon, Gyeongnam 641-773, Republic of Korea
School of Materials Science and Engineering, Changwon National University, Changwon, Gyeongnam 641-773, Republic of Korea
Advanced Analysis Center, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 5 October 2014
Received in revised form 29 January 2015
Accepted 6 February 2015
Available online 9 February 2015

We reported structural, magnetic and electronic structure studies of Co doped ZnO nanoparticles. Doping
of Co ions in ZnO host matrix has been studied and conrmed using various methods; such as X-ray
diffraction (XRD), eld emission scanning electron microscopy (FE-SEM), energy dispersed X-ray (EDX),
high resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy
(FT-IR), near edge X-ray absorption ne structure (NEXAFS) spectroscopy, magnetic hysteresis loop
measurements and X-ray magnetic circular dichroism (XMCD). From the XRD and HR-TEM results, it is
observed that Co doped ZnO nanoparticles have single phase nature with wurtzite structure and exclude
the possibility of secondary phase formation. FE-SEM and TEM micrographs show that pure and Co doped
nanoparticles are nearly spherical in shape. O K edge NEXAFS spectra indicate that O vacancies increase
with Co doping. The Co L3,2 edge NEXAFS spectra revealed that Co ions are in 2+ valence state. DC
magnetization hysteresis loops and XMCD results clearly showed the intrinsic origin of temperature
ferromagnetism in Co doped ZnO nanoparticles.
2015 Elsevier Ltd. All rights reserved.

PACS:
75.50.Pp
18.70.Dm
61.46. +w
82.80.Ej
Keywords:
Electronic material
Nanostructures
Chemical synthesis
XANES
Magnetic properties

1. Introduction
During the last decades dilute magnetic semiconductors
(DMSs) have inspired a great deal of attention due to their
underlying fundamental physics and their potential application in
second generation of spin electronic devices: such as spin light
emitting diodes, non-volatile memory, logic devices, spin valve
transistor and optical isolator etc. [14]. DMSs could pave the way
to exploit the charge and spin of the carrier in spintronics devices
and the combination of these two degree of freedom promises the
new functionality in the devices. The practical device needs the
suitable ferromagnetic semiconductors, which allow the simultaneous control of the charge and spin state of the electron at room
temperature. This phenomenon can be realized by introducing the
magnetism in a semiconducting materials. Therefore, the magnetic
properties of DMSs can be tailored by replacing a fraction of the
cation of the host semiconducting materials by the transition

* Corresponding authors. Tel.: +82 55 213 3890; fax: +82 55 262 6486.
E-mail addresses: shailuphy@gmail.com (S. Kumar), tksong@changwon.ac.kr
(T.K. Song).
http://dx.doi.org/10.1016/j.materresbull.2015.02.020
0025-5408/ 2015 Elsevier Ltd. All rights reserved.

metal (TM) ions. Till now the magnetic properties of various TM

ions doped compound semiconductors such as ZnO, TiO2, SnO2,
CeO2, etc. [519] doped with TM ions have been studied. Sharma
et al. reported the RT-FM in Co doped SnO2 nanoparticles prepared
by the co-precipitation method [6]. Kumar et al. also reported the
RT-FM in Mn doped TiO2 thin lms prepared by the pulsed laser
deposition method [12]. Moreover, Ahmed et al. fabricated the TM
doped ZnO nanostructures by the microwave assisted solution
route and reported the detailed investigation of structural,
magnetic, optical properties of these nanostructures [10]. Sharma
et al. also claimed the RT-FM in Fe doped CeO2 thin lms prepared
by the pulsed laser deposition method. The experimental
observation about the nature of the magnetic properties of DMSs
synthesized by different methods are controversial [2025]. It is
observed that the DMSs prepared using different methods exhibit
distinctively different magnetic properties, ranging from paramagnetism to high temperature ferromagnetism [22,2628].
Bouloudenine et al. reported the antiferromagnetism in Co doped
ZnO bulk samples prepared by the co-precipitation route, whereas
Lawes et al. claimed the absence of the ferromagnetism in Co and
Mn substituted ZnO. These highly contradictory experimental
results are probably associated with different defects or impurities

S. Kumar et al. / Materials Research Bulletin 66 (2015) 7682

created by different preparation methods. Venkatesan et al. [29]

have studied a correlation between the magnitude of magnetic
moments with the oxygen partial pressure during annealing, and
they observed that annealing in higher oxygen partial pressure
reduces the amount of magnetization. Kumar et al. [21] also
claimed the RT-FM in pure ZnO nanorods due to the oxygen
vacancies. Therefore, from the reported literature it clear that
defects play a crucial role in ferromagnetic ordering in DMSs.
Herein, we have chosen ZnO as a host semiconductor. ZnO is an
interesting direct band gap (3.27 eV) semiconductor, which is
explored for various applications in optoelectronics. Therefore, the
incorporation of ferromagnetism in ZnO can lead to a diversity of
new multifunctional devices. However, in spite of being one of the
most representative and widely investigated material, Co doped
ZnO still lacks clear explanation about the ferromagnetism at room
temperature. Despite of extensive efforts in this area, still there has
been a great deal of controversy, particularly on fundamental
issues such as the origins and characteristics of the observed
ferromagnetism (FM).
In this work, we report the ferromagnetism in the Co doped ZnO
nanoparticles at room temperature. We have performed a
systematic investigation of the structure and magnetic properties
using various methods. X-ray diffraction (XRD), high resolution
transmission electron microscopy (HR-TEM) and Fourier transform
infrared spectroscopy (FT-IR) measurements demonstrate that Co
doped ZnO nanoparticles exhibit a single phase nature with
wurtzite lattice and ruled out the formation of any impurity phase.
NEXAFS measurements performed at Co L3,2-edge clearly shows
the absence of Co clusters and also reveals that Co ions are in 2+
valance state. DC magnetization and XMCD measurements showed
that Co doped ZnO nanoparticles exhibits RT-FM.
2. Experimental
Zn1
xCoxO (x = 0.00, 0.01, and 0.03) nanoparticles were
prepared by co-precipitation technique using Zn(NO3)26H2O
and Co(NO3)26H2O. The precursor of zinc and cobalt nitrates
(purity 99.99% from Aldrich) was employed to make Co doped ZnO
nanoparticles. These metal nitrates were dissolved in de-ionized
water to get a 0.06 M solution and then kept for stirring for 1 h. In
this solution, NH4OH solution was added drop wise until the pH of
solution reached to 8. This mixture was stirred for 3 h at room
temperature and after that washed 5 times with de-ionized water
and ethanol. The precipitate obtained after wash was dried at
100  C for 12 h. Finally, the dried samples were ground and kept for
calcination at 500  C for 4 h. Thermal gravimetric (TG) and
differential thermal (DT) measurements were performed using
2960 SDT TA instrument. Philips X-pert X-ray diffractometer with
Cu Ka (l = 1.5405 ) was used to study single phase nature of the
Zn1
xCoxO (x = 0.00, 0.01, and 0.03) nanoparticles at room
temperature. The surface morphology of pure and Co doped
ZnO nanoparticles was studied by using FE-SEM (Mira II LHM) at an
accelerating voltage 200 kV with an attached energy dispersed
X-ray (EDX) spectrometer. Before the FE-SEM measurements, a
small quantity of powder was dissolved in acetone and put for
10 min in ultrasonic bath and then few drops of this solution were
disperse on glass slide. The glass slide was then dried at 80  C for
half an hour. Finally, the glass slide dispersed with nanoparticles
was coated with platinum to avoid the charging effect during the
measurements. TEM image and HR-TEM measurements were
performed using FE-TEM (JEOL/JEM 2100F). For TEM measurements the nanoparticles of Co doped ZnO were dispersed
homogeneously in ethanol using ultrasonic treatment. A minute
drop of this solution was cast on to a carbon-coated copper grid
followed by subsequently drying in air before transfer it in to
microscope. FT-IR measurements were performed using Nicolet

77

Impact 410DSP spectrometer. The XMCD experiment for 3% Co

doped ZnO was performed at 2A MS beam line of Pohang
Accelerator Laboratory (PAL) operating at 3 GeV with a maximum
storage current of 300 mA. This beam line has elliptically polarized
undulator with greater than 90% degree of circular polarization.
The XMCD spectrum was taken for a xed helicity of the light by
reversing the applied magnetic eld (0.8T) for each hn. The
spectrum was normalized to the incident photon ux. The NEXAFS
measurements of pure and Co doped ZnO along with the reference
compounds of Co3O4 and CoO at O K and Co L3,2-edge were
performed at the soft X-ray beam line 10D KIST of PAL. The spectra
were simultaneously collected in the total electron yield (TEY)
mode and the uorescence yield (FY) mode at room temperature in
a vacuum 1.5  10
8 Torr. The spectra in the two modes turned
out to be nearly identical indicating that the systems are so stable
that the surface contamination effects are negligible even in the
TEY mode. The spectra were normalized to incident photon ux
and the energy resolution was 0.2 eV. Magnetic hysteresis loop
measurements were performed at room temperature using a
commercial Quantum Design physical properties measurement
system (PPMS).
3. Results and discussion
Thermal gravimetric (TG) and differential thermal (DT) analysis
of the as synthesized samples of Co doped ZnO nanoparticles were
carried out to determine the weight loss process and approximate
calcinations temperature. The precipitate obtained after washed
by the distilled water and ethanol was dried at 100  C. The dried
samples again need the thermal treatment to form the metal oxide
powder. DT-TGA curve for 3% Co doped ZnO nanoparticles is shown
in Fig. 1. The as synthesized Co doped ZnO nanoparticles were
heated up to 1000  C in the nitrogen atmosphere at a rate of 10  C/
min. It is clear from Fig. 1 that DTA peak closely corresponds to the
weight changes observed in the TGA curve. It is observed that the
thermal decomposition of the dried sample occurs in three steps
below 400  C. The rst stage of the decomposition was observed in
the temperature range 40108  C with an endothermic peak at
96.9  C, that indicates a weight loss of 8.7%, which may be due to
the evaporation of ethanol. The second and third stages of the
decomposition were found in the temperature range 122154  C
and 200400  C, respectively. The weight losses in the second and
third stages were 3.4% and 28.7%, respectively. The weight loss
observed in the second stage may be due to the evaporation of the
water content. However, the weight loss noticed in the third stage

[(Fig._1)TD$IG]

Fig. 1. TGA and DTA curve of Zn0.97Co0.03O nanoparticles.

78

S. Kumar et al. / Materials Research Bulletin 66 (2015) 7682

is due to the decomposition of the ZnCo precursor to the

formation of Zn0.97Co0.03O. Since, there is no signicant change in
the weight loss above the 400  C, the calcination temperature of
the powders was decided to be over 400  C.
Powder XRD pattern obtained from Zn1
xCoxO (0.00  x  0.03)
nanoparticles are shown in Fig. 2. The XRD data were analyzed and
indexed using Powder-X [30] software. It can be seen from the XRD
pattern that all the samples have a single phase nature with
hexagonal wurtzite structure. No Co cluster or Co related complex
was detected, at least within the sensitivity of X-ray diffaractometer, which ruled out the possibility of any secondary phase.
The full width at half maximum calculated using (0 0 2) peaks has
been found to increase as increasing the Co content. Moreover, the
position of the XRD peak corresponding to the (0 0 2) plane is found
to shift towards lower 2u value with increasing the Co contents.
The d (lattice spacing) values from (0 0 2) peak have been plotted as
a function of Co contents is shown in the inset of Fig. 2. It is
observed that the d (0 0 2) value increases linearly with the Co
content which is consistent with the results reported by the other
groups on this system [31,32]. A linear increase of the lattice
spacing thus reects, in accordance with Vegards law.
FT-IR measurements of Co doped ZnO nanoparticles have been
carried out to examine the change in ZnO bonding due to the Co
substitution. FT-IR measurements performed in the wavenumber
range 4004000 cm
1 using KBr method at RT are shown in Fig. 3.
It is observed that undoped and Co doped ZnO nanoparticles
exhibited the absorption band at 3450, 1620, 1080, 867,
700, 500 and 425 cm
1 and which are well matched with
earlier reported results [3335]. The absorption peak appeared at
3450 cm
1 is attributed to normal polymeric OH stretching
vibration of H2O in CoZnO lattice [34], which might be due to the

[(Fig._2)TD$IG]

Fig. 2. XRD pattern of Zn1
xCoxO (x = 0.00, 0.01 and 0.03) nanoparticles. Inset-1
shows the d (0 0 2) value as a function of Co content and inset-2 represents the
FWHM as function of Co content.

[(Fig._3)TD$IG]

Fig. 3. FTIR spectra of Zn1
xCoxO (x = 0.0, 0.01 and 0.03) nanoparticles.

adsorption of moisture, when FT-IR sample disks were prepared in

an open air atmosphere. Another weak intense peak at 1620 cm
1
is assigned to HOH bending vibration mode, which is due to a
small amount of H2O in the ZnO nanoparticles [35]. The absorption
bands 1080 cm
1 may be originated due to asymmetric stretching of resonance interaction between vibration modes of oxide ions
in nanomaterials [33]. The absorption bands at 500 and
425 cm
1 are attributed to the ZnO stretching in the ZnO
lattice. The absorption bands in the range of 425410 cm
1
correspond to the E2 mode of the hexagonal ZnO (Raman active).
However, the absorption bands in 506493 cm
1 range may be
associated with oxygen deciency and/or oxygen vacancy defect in
ZnO [36]. Although, in case of undoped ZnO nanoparticles, we
observed these two strong absorption bands at 425 and 506 cm
1,
but in case of 1% Co doped ZnO nanoparticles, the value of
absorption bands was found at 419 and 498 cm
1, whereas for 3%
Co doped ZnO nanoparticles, these values were at 410 and
496 cm
1, respectively. It can be clearly seen from the FT-IR
measurements that these absorption bands have blue shift with Co
doping. The shift in the peak position of ZnO absorption bands is
suggestive of the fact that ZnOZn network is perturbed by the
presence of Co in ZnO host matrix. Thus, from FT-IR results, it may
be concluded that Co ions are occupying Zn position in ZnO matrix
which are consistent with the results as observed in XRD
measurements.
The morphology and chemical composition of pure and Co
doped ZnO nanoparticles were investigated by FE-SEM and EDX
measurements. From the FE-SEM micrograph (not shown here due
to the brevity of article), it is observed that all the particles are
nearly spherical in shape. Fig. 4(a) and (b) highlights the typical
EDX spectra taken from pure and 3% Co-doped ZnO samples. The
chemical analysis of Zn1
xCoxO nanoparticles for x = 0.00 and 0.03
measured by EDX analysis shows the presence of Zn, O and Co only.
The EDX results indicate that the nanoparticles of pure ZnO are
made up of zinc, oxygen ions only whereas Co doped ZnO have Zn,
O and Co ions only.
In order to get more insight of the structural properties, we had
also performed high resolution transmission electron microscopy
(HR-TEM) measurements. Fig. 5(a) and (c) represents TEM
micrograph of pure and 3% Co doped ZnO. It can be clearly seen
from TEM micrographs that particles are agglomerated. TEM
micrograph indicates the nano-crystalline behavior of the samples
with almost spherical shape which are in good agreement with the
FE-SEM results. In order see the particle size distribution, the

S. Kumar et al. / Materials Research Bulletin 66 (2015) 7682

[(Fig._4)TD$IG]

79

Fig. 4. EDX spectrum of (a) ZnO and (b) Zn0.99Co0.01O nanoparticles.

particle size was measured by using Image-J software. The mean

particle size calculated using the Lorentzian tting (see Fig. 5(b)
and (d)) of the histograms was found 16.5 and 14.0 nm for pure and
3% Co doped ZnO, respectively. The particle size obtained from the
TEM micrographs infer that Co doping hindered the particle
growth of Co-doped ZnO which are in good agreement with the
XRD results. Furthermore, to see any impurity phase in doped

[(Fig._5)TD$IG]

samples, we have performed HR-TEM measurements of pure and

Co doped ZnO nanoparticles. HR-TEM images were taken at
different part of the samples, to investigate the presence of any
secondary phase related to Co in doped ZnO nanoparticles. Inset in
Fig. 5(a) and (c) shows the HR-TEM image of pure and 3% Co doped
ZnO nanoparticles. A careful analysis of the inter-planer distance
calculated from HR-TEM image shows the (1 0 0) planes of

Fig. 5. TEM micrograph of (a) ZnO and (c) Zn0.97Co0.03O nanoparticles. Insets in (a) and (c) show high resolution TEM image. Insets in (b) and (d) show the particle size
distribution histogram.

80

S. Kumar et al. / Materials Research Bulletin 66 (2015) 7682

hexagonal structure of ZnO. HR-TEM image taken on the samples

with different Co concentration also indicates that individual
nanoparticle has single phase nature. HR-TEM observations of
large number of randomly selected particles showed the absence of
impurity phase and suggesting their good crystallinity.
The NEXAFS techniques have been established as a powerful
tool to understand the local structure of the transition metal doped
various oxide systems. The spectral features in NEXAFS spectra are
very sensitive to the symmetry of the probed ions as well as local
environment. The peak position and spectral features of the
NEXAFS spectra are affected not only by the oxidation state of
probed ion, but also by its structural symmetry and covalent/ionic
character of the bonds between cations and neighboring atoms. In
NEXAFS experiment, the photons of characteristic energies are
absorbed to produce the transition of a core electron to an empty
state above the Fermi level and are governed by the dipole
selection rules. Fig. 6 illustrates O K-edge NEXAFS spectra of
Zn1
xCoxO nanoparticles. Basically the O K-edge spectra originate
due to a transition from O 1s core state to the unoccupied O 2p
derived states, which are hybridized states with the moderately
narrow 3d band and broader 4sp bands of the 3d transition metal
ions. The spectral feature in the energy range of 530539 eV can be
ascribed to the hybridization between O 2p and Zn and Co 4s states
followed by the region between 540 and 550 eV, which is due to
the hybridization between O 2p and Zn and Co 4p states. The
spectral feature above 550 eV is due to the hybridization between
O 2p and Zn and Co 4d states. By comparing the NEXAFS spectra of
Co doped ZnO nanoparticles with undoped ZnO nanoparticles, it is
observed that the some extra spectral feature evolve at 528
(marked by a) and 532 eV (marked by b) and its intensity increases
with Co doping. The new feature appeared at 532 eV, nearby the
conduction-band minimum, can be assigned to the cobalt 3d and O

[(Fig._6)TD$IG]

[(Fig._7)TD$IG]

Fig. 7. MH hysteresis loop of Zn0.99Co0.01O nanoparticles at different temperature.

Inset showing the expanded view of low eld region.

2p hybridized states. Furthermore, the broadening of the spectral

features observed in doped samples at 535 eV (b) is thought to be
due to the presence of the oxygen vacancies. Thus, increase in
broadening of spectral features at 535 eV infer that Co atoms are
occupying the interstitial site of the ZnO matrix surrounded by the
oxygen. Therefore, we may say that Co ions are coordinated with
oxygen site tetrahedrally in ZnO. The broadening of the spectral
features observed for 3% Co doped ZnO nanoparticles is higher in
comparison to other composition at 535 eV. The broadening is
assigned due to the presence of the oxygen vacancies indicating
that the oxygen-related defect concentration is higher in 3% cobalt
doped ZnO nanoparticles. This may be the reason that 3% doped
sample shows the higher magnetic moment in comparison to other
composition.
Lots of controversies have been reported in the literature about
the origin of ferromagnetism in Co doped ZnO. So in order to check
the role of Co doping and origin of ferromagnetism, we have
performed NEXAFS and XMCD measurements at Co L3,2-edge of Co
doped ZnO nanoparticles. NEXAFS is a very effective tool to conrm
the secondary phase such as Co clusters, Co oxide phase or whether

[(Fig._8)TD$IG]

Fig. 6. NEXAFS spectra measured at the O K-edge for Zn1
xCoxO (x = 0.00, 0.01, and
0.03) nanoparticles. Inset-1 shows the NEXAFS spectra measured at Co L3,2-edge of
Zn1
xCoxO (x = 0.01, and 0.03) nanoparticles. Inset-2 shows the XMCD spectrum of
Zn0.97Co0.03O nanoparticles measured at Co L3,2-edge.

Fig. 8. MH hysteresis loop of Zn0.97Co0.03O nanoparticles at different temperature.

Inset showing the expanded view of low eld region.

S. Kumar et al. / Materials Research Bulletin 66 (2015) 7682

81

Table 1
Calculated value of coercive eld (HC), remanent magnetization (Mr) and saturation magnetization (MS) for Zn1
xCoxO2 (x = 0.01 and 0.03) nanoparticles at different
temperature.
Sample

Temperature (K)

Coercive eld (HC) (Oe)

Remanence magnetization (Mr)  10
4 (emu/g)

Zn0.99Co0.01O

100
200
300

50
40.6
35.8

4.41
3.9
3.3

6.4
6.4
6.3

Zn0.97Co0.03O

100
200
300

60.4
32.2
28.8

7.2
4.43
3.72

10.7
9.7
9.2

it is substituting Co at Zn position in the ZnO nanoparticles or not.

Inset-1 in Fig. 6 shows the Co L3,2-edge NEXAFS spectra of Co doped
ZnO nanoparticles at room temperature. It is clear from the inset
that the spectral features of Co L3,2-edge are neither similar to
Co3O4 nor Co metal [3739]. The Co L3,2-edge spectral features
result from the Co 2p ! 3d dipole transitions and are strongly
inuenced by the large 2p core-hole spin coupling energy which
divide the spectra into L3 and L2 regions at low and high photon
energies, respectively. In comparison with the spectrum of Co
metal, Co3O4 and CoO, one can see that the spectra of Co doped ZnO
nanoparticles are very similar to the CoO, which show that the Co
ions are in 2+ valance state in Co doped ZnO nanoparticles.
XMCD measurements were also performed to know about the
source of room temperature ferromagnetism in Co doped ZnO
nanoparticles. The magnetization of the sample is proportional to
the XMCD signal, which results from the difference between XAS
spectrum recorded for the parallel (m+) and antiparallel (m
)
alignment of the photon helicity with applied led. Inset in Fig. 6
shows the XMCD spectrum of 3% Co doped ZnO nanoparticles. It
can be clearly seen from the XMCD (m+m+) signal with a negative
sign at energy (hv) 777.5 eV conrm the intrinsic origin of
ferromagnetism in the Co doped ZnO nanoparticles. The XMCD
signal observed at 777.5 eV indicated that ferromagnetism is due to
Co2+ ion, which also conrm that Co ions are in 2+ valence state in
ZnO matrix.
Magnetic hysteresis loop measurements of Zn1
xCoxO (x = 0.01
and 0.03) with different Co doping have been performed at
different temperature. Figs. 7 and 8 show the magnetization versus
eld (MH) curves for 1% and 3% Co doped ZnO nanoparticles at
different temperature (temperature range (100300 K)), which
infers that all the samples exhibit ferromagnetic behavior with TC
above the room temperature. The deduced value of coercive eld
and remanence magnetization is shown in Table 1. It is observed
that the value of coercive eld and remenance magnetization
decreases with increase in the temperature for both the sample. It
can be seen from the hysteresis loops measurements measured at
100, 200 and 300 K that the value of the saturation magnetization
is almost same, except the slight higher value of HC and Mr at low
temperatures (see Table 1). Moreover, it is observed that the
saturation magnetization value of 3% doped samples is higher than
1% Co doped ZnO. However, the value of the magnetic moment is
found to be very small in the present case. Some groups have
reported that small value of the moments in DMSs may originate
due to the presence of the additional antiferromagnetic type
coupling between some neighboring ions [23,40]. As a result, this
antiferromagnetic coupling may lead to the canting of the spin.
Hence, the observed weak FM in Co doped ZnO nanoparticles is an
intrinsic property and is not due to the ferromagnetism of Co
clusters as supported by our XRD, FTIR, HRTEM and NEXAFS
spectroscopy results. Moreover, in addition to the magnetic doping
effect, the oxygen vacancies have been found to play an important
role in the RTFM for Co doped ZnO nanoparticles. Some theoretical
groups have reported that magnetic ordering in DMSs can be
tailored by creating the oxygen vacancies, because oxygen

Saturation magnetization (MS)  10
3 (emu/g)

vacancies can cause a noticeable change in the band structure of

the host matrix [41,42]. From the O K-edge spectra, it is observed
that an oxygen vacancy increases with Co doping, which may
increase the magnetic moment of the system. The bound magnetic
polarons (BMPs) model may be applied to explain the observed
ferromagnetism in the present case. According to BMP model, the
oxygen vacancies locally exist around magnetic ions i.e., Co ions
substitute for Zn in ZnO matrix. An electron trapped by the oxygen
vacancies undergo orbital coupling with the d shells of the adjacent
Co2+ ions and form the BMPs. In each BMP, the neighboring Co2+
cations create a spin-alignment of Co2+/Co2+ magnetic exchange
coupling. When a large number of BMPs overlap, a continuous
chain of Co2+/Co2+ magnetic exchange coupling is shaped, and
ferromagnetic ordering in Co doped ZnO is established. A higher
density of oxygen vacancies results in a greater overall volume
being occupied by BMPs, thereby, increasing the probability of
overlapping more Co ions into the ferromagnetic domains, which
will enhance the ferromagnetism [43].
4. Conclusions
We have successfully synthesized single phase Co doped ZnO
nanoparticles. From XRD pattern, HR-TEM and FTIR measurements, it is observed that Co ions are occupying the Zn position in
ZnO matrix. NEXAFS measurements infer the absence of Co metals
clusters and the observed spectral features are similar to the CoO,
which indicates that Co ions are in 2+ valence state. The DC
magnetization and XMCD measurements clearly reect Co doped
ZnO nanoparticles exhibits intrinsic ferromagnetism at room
temperature.
Acknowledgements
This work was supported by the Priority Research Centers
Program through the National Research Foundation of Korea (NRF)
funded by the MOE (2012-045424) and by the National Research
Foundation of Korea [KRF] grant funded by the Korea government
[MSIP] (2012-0009457).
References
[1] T. Fukumura, Z. Jin, A. Ohtomo, H. Koinuma, M. Kawasaki, Appl. Phys. Lett. 75
(1999) 3366.
[2] S.W. Jung, S.-J. An, G.-C. Yi, C.U. Jung, S.-I. Lee, S. Cho, Appl. Phys. Lett. 80 (2002)
4561.
[3] H. Ohno, Science 281 (1998) 951.
[4] S. Gayathri, O. Sivaraman, N. Ghosh, S. Sathishkumar, J. Jayaramudu, S.S. Ray, A.
K. Viswanath, Appl. Sci. Lett. 1 (2015) 8.
[5] S. Kumar, B.H. Koo, S.K. Sharma, M. Knobel, C.G. Lee, Nano 05 (2010) 349.
[6] A. Sharma, A.P. Singh, P. Thakur, N.B. Brookes, S. Kumar, C.G. Lee, R.J.
Choudhary, K.D. Verma, R. Kumar, J. Appl. Phys. 107 (2010) .
[7] S. Kumar, B.H. Koo, C.G. Lee, S. Gautam, K.H. Chae, S.K. Sharma, M. Knobel,
Funct. Mater. Lett. 04 (2011) 17.
[8] F. Ahmed, S. Kumar, N. Arshi, M.S. Anwar, B.H. Koo, C.G. Lee, Funct. Mater. Lett.
04 (2011) 1.
[9] S. Kumar, F. Ahmed, M.S. Anwar, H.K. Choi, H. Chung, B.H. Koo, Mater. Res. Bull.
47 (2012) 2980.

82

S. Kumar et al. / Materials Research Bulletin 66 (2015) 7682

[10] F. Ahmed, S. Kumar, N. Arshi, M.S. Anwar, S.N. Heo, B.H. Koo, Acta Mater. 60
(2012) 5190.
[11] M.S. Anwar, S. Kumar, F. Ahmed, N. Arshi, G.-S. Kil, D.-W. Park, J. Chang, B.H.
Koo, Mater. Lett. 65 (2011) 3098.
[12] S. Kumar, S. Gautam, G.W. Kim, F. Ahmed, M.S. Anwar, K.H. Chae, H.K. Choi, H.
Chung, B.H. Koo, Appl. Surf. Sci. 257 (2011) 10557.
[13] R. Prakash, S. Kumar, F. Ahmed, C.G. Lee, J. Il Song, Thin Solid Films 519 (2011)
8243.
[14] F. Ahmed, S. Kumar, N. Arshi, M.S. Anwar, B.H. Koo, C.G. Lee, Thin Solid Films
519 (2011) 8199.
[15] S.K. Sharma, P. Thakur, S. Kumar, D.K. Shukla, N.B. Brookes, C.G. Lee, K.R. Pirota,
B.H. Koo, M. Knobel, Thin Solid Films 519 (2010) 410.
[16] F. Ahmed, S. Kumar, N. Arshi, M.S. Anwar, B.H. Koo, C.G. Lee, Microelectron. Eng.
89 (2012) 129.
[17] S. Kumar, Y.J. Kim, B.H. Koo, C.G. Lee, J. Nanosci. Nanotechnol. 10 (2010) 7204.
[18] F. Ahmed, S. Kumar, N. Arshi, M.S. Anwar, G.W. Kim, S.N. Heo, E.S. Byon, S.H.N.J.
Lee Lyu, B.H. Koo, J. Nanosci. Nanotechnol. 12 (n.d (2015) 5464.
[19] M. Varshney, A. Sharma, K.H. Chae, S. Gautam, H.J. Shin, Appl. Sci. Lett. 1 (2015)
19.
[20] M.H. Kane, K. Shalini, C.J. Summers, R. Varatharajan, J. Nause, C.R. Vestal, Z.J.
Zhang, I.T. Ferguson, J. Appl. Phys. 97 (2005) 23906.
[21] S. Kumar, Y.J. Kim, B.H. Koo, S. Gautam, K.H. Chae, R. Kumar, C.G. Lee, Mater.
Lett. 63 (2009) 194.
[22] G. Lawes, A. Risbud, A. Ramirez, R. Seshadri, Phys. Rev. B 71 (2005) 45201.
[23] M. Bouloudenine, N. Viart, S. Colis, J. Kortus, A. Dinia, Appl. Phys. Lett. 87 (2005)
525501.
[24] S. Kumar, Y.J. Kim, B.H. Koo, S.K. Sharma, J.M. Vargas, M. Knobel, S. Gautam, K.H.
Chae, D.K. Kim, Y.K. Kim, C.G. Lee, J. Appl. Phys. 105 (2009) .
[25] F. Ahmed, S. Kkumar, N. Arshi, M.S. Anwar, B.H. Koo, C.G. Lee, Int. J. Nanosci. 10
(2011) 1025.
[26] Y.P. Zhang, S.-S. Yan, Y.-H. Liu, M.-J. Ren, Y. Fang, Y.X. Chen, G.L. Liu, L.M. Mei, J.P.
Liu, J.H. Qiu, S.Y. Wang, L.Y. Chen, Appl. Phys. Lett. 89 (2006) 42501.

[27] J.H. Yang, Y. Cheng, Y. Liu, X. Ding, Y.X. Wang, Y.J. Zhang, H.L. Liu, Solid State
Commun. 149 (2009) 1164.
[28] L.Q. Liu, B. Xiang, X.Z. Zhang, Y. Zhang, D.P. Yu, Appl. Phys. Lett. 88 (2006)
63104.
[29] M. Venkatesan, C.B. Fitzgerald, J.G. Lunney, J.M.D. Coey, Phys. Rev. Lett. 93
(2004) 177206.
[30] C. Dong, J. Appl. Crystallogr. 32 (1999) 838.
[31] S. Kumar, S. Gautam, Y.J. Kim, B.H. Koo, K.H. Chae, C.G. Lee, J. Ceram. Soc. Japan
117 (2009) 616.
[32] M. Naeem, S.K. Hasanain, M. Kobayashi, Y. Ishida, S. a Fujimori, Buzby, S.I. Shah,
Nanotechnology 17 (2006) 2675.
[33] V. Gandhi, R. Ganesan, H. Hameed, A. Syedahamed, M. Thaiyan, J. Phys. Chem. C
118 (2014) 9715.
[34] A.J. Reddy, M.K. Kokila, H. Nagabhushana, R.P.S. Chakradhar, C. Shivakumara, J.
L. Rao, B.M. Nagabhushana, J. Alloys Compd. 509 (2011) 5349.
[35] S. Muthukumaran, R. Gopalakrishnan, Opt. Mater. (Amst.) 34 (2012) 1946.
[36] A. Kaschner, U. Haboeck, M. Strassburg, M. Strassburg, G. Kaczmarczyk, A.
Hoffmann, C. Thomsen, A. Zeuner, H.R. Alves, D.M. Hofmann, B.K. Meyer, Appl.
Phys. Lett. 80 (2002) 1909.
[37] A.P. Singh, R. Kumar, P. Thakur, N.B. Brookes, K.H. Chae, W.K. Choi, J. Phys.
Condens. Matter 21 (2009) 185005.
[38] S. Krishnamurthy, C. McGuinness, L.S. Dorneles, M. Venkatesan, J.M.D. Coey, J.
G. Lunney, C.H. Patterson, K.E. Smith, T. Learmonth, P.-A. Glans, T. Schmitt, J.-H.
Guo, J. Appl. Phys. 99 (2006) 08M111.
[39] S. Gautam, P. Thakur, P. Bazylewski, R. Bauer, A.P. Singh, J.Y. Kim, M.
Subramanian, R. Jayavel, K. Asokan, K.H. Chae, G.S. Chang, Mater. Chem. Phys.
140 (2013) 130.
[40] H. Ohno, J. Magn. Magn. Mater. 200 (1999) 110.
[41] J.E. Jaffe, T.C. Droubay, S.A. Chambers, J. Appl. Phys. 97 (2005) 73908.
[42] H. Weng, X. Yang, J. Dong, H. Mizuseki, M. Kawasaki, Y. Kawazoe, Phys. Rev. B 69
(2004) 125219.
[43] J.M.D. Coey, M. Venkatesan, C.B. Fitzgerald, Nat. Mater. 4 (2005) 173.