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Competing effects of Cu ionic charge and oxygen vacancies on the ferromagnetism of (Zn,

Co)O nanoparticles

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2008 J. Phys.: Condens. Matter 20 255223

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IOP PUBLISHING JOURNAL OF PHYSICS: CONDENSED MATTER
J. Phys.: Condens. Matter 20 (2008) 255223 (7pp) doi:10.1088/0953-8984/20/25/255223

Competing effects of Cu ionic charge and

oxygen vacancies on the ferromagnetism
of (Zn, Co)O nanoparticles
M Naeem1 , S K Hasanain1 , Sabeen Sher Afgan1 and
Abdul Rumaiz2
1
Magnetism and Superconductivity Group, Department of Physics, Quaid-i-Azam University,
Islamabad, Pakistan
2
Department of Physics and Astronomy, University of Delaware, Newark, DE 19716, USA

E-mail: [email protected]

Received 27 March 2008

Published 21 May 2008
Online at stacks.iop.org/JPhysCM/20/255223

Abstract
We report the effects on the ferromagnetism due to co-doping of ZnO with Co and Cu in the
presence of variable numbers of oxygen vacancies. The co-doped nanoparticles
Zn0.95− Co0.05Cuy O (0.00  y < 0.009) were prepared via the chemical route with oxygen
vacancies introduced via annealing in a reducing atmosphere for variable amounts of time. In
addition to the magnetization, the particles were characterized by x-ray diffraction (XRD), x-ray
photoemission spectroscopy (XPS) and x-ray absorption near edge spectroscopy (XANES). The
Co ions were determined to be in the +2 state in a tetrahedral symmetry, with no evidence for
metallic Co or Cu. However, the ionic state of Cu is found to change from +2 to +1 state with
increasing Cu concentration, which appears to strongly decrease the concentration of oxygen
vacancies. It is found that the ferromagnetic moment initially increases with the addition of Cu
but decreases above a typical concentration that coincides with the appearance of the Cu+1 state
and the decrease of O vacancy concentration. It is concluded that the effect of Cu in the very
low range of concentrations, where it appears to go in as Cu+2 , is to stabilize ferromagnetism
indirectly via generation of O vacancies. The effects of O vacancy concentration on the
ferromagnetism are interpreted in the light of the F-center exchange (FCE) model.
(Some figures in this article are in colour only in the electronic version)

1. Introduction electronics’ [6–9], which could pave the way to exploit the spin
as well as charge of the carrier in semiconductor devices. The
The semiconductor ZnO has received substantial interest in stabilization or enhancement of ferromagnetic (FM) properties
the research community because of its wide direct band gap by co-doping of ions has been predicted theoretically [10–12]
(3.3 eV) and large exciton binding energy (60 meV) which and confirmed by some experiments [13–15]. Sato et al
could lead to lasing action based on exciton recombination [10] used first principles calculations to reveal that Mn-doped
even above room temperature [1]. It is a well known ZnO changed its magnetic state from spin-glass to FM with
piezo-electric [2] and electro-optic material [3] with potential increasing hole concentration. Spaldin et al [11] predicted
applications such as opto-electronic and luminescent devices as using the density functional theory (DFT) approach that p-
well chemical sensors [4]. Even though the research focusing type doping in (Zn, Co)O could strongly stabilize the FM state.
on ZnO goes back several decades, one of the renewed Bergqvist et al [12] combining first principles calculations of
interests is fueled by the observation of ferromagnetism interatomic exchange interactions with a Heisenberg model
in transition metal (TM) doped ZnO labeled as a diluted and Monte Carlo simulations, have explained the preparation
magnetic semiconductor (DMS) [5]. DMSs have inspired a dependence of ferromagnetism in TM doped diluted magnetic
great deal of research interest in the field of ‘magneto-opto- semiconductors as due to the random ordering of magnetic

0953-8984/08/255223+07$30.00 1 © 2008 IOP Publishing Ltd Printed in the UK

J. Phys.: Condens. Matter 20 (2008) 255223 M Naeem et al

ions and distribution of defects. Experimentally, Yan et al

[14] reported that the (Mn, Co) co-doped ZnO films with
high resistance showed room temperature ferromagnetism,
and the co-doping of (Mn, Co) results in an increase of
the saturated magnetic moments. Han et al [15] found that
the FM properties of Zn1−x Fe x O thin films are enhanced by
the co-doping of Cu as an acceptor impurity. On the basis
of theoretical calculations and experimental supports, it has
been predicted that p-type doping in ZnO should be more
effective to produce FM properties than that of n-type doping.
Buchholz et al [16] have shown that Cu-doped thin films with
n-type ZnO were non-magnetic while p-type ZnO films doped
with Cu were ferromagnetic at room temperature. However, Figure 1. X-ray diffraction patterns of Zn0.95−y Co0.05 Cu y O
it is generally accepted that the growth of p-type ZnO is (0  y  0.0087). Peaks are indexed to the hexagonal wurtzite
still an experimental challenge due to self-compensation from structure.
oxygen vacancies [17] or the incorporation of hydrogen as an
unintentional donor [18].
In view of the competing effects of on the one hand O nature of the products, x-ray diffraction (XRD) studies were
vacancies, as an effective n-type dopant, and on the other hand, conducted, while the charge states of the different dopants, the
the role of Cu in stabilizing the FM in ZnO but in p-type absence of metallic clusters and relative vacancy concentration
conditions, we have explored the combined effects of these of different samples was inferred from x-ray photoemission
two variables namely O vacancies and Cu dopants. While co- spectroscopy (XPS). Some selected x-ray absorption near
doping studies of Co–Cu in ZnO have been reported in the edge structure (XANES) measurements were also performed
literature these have only been in the high Cu concentration to augment the XPS derived information. Magnetization
range where Cu itself bears a magnetic moment. However, studies were carried out on a commercial vibrating sample
the behavior of Cu in the ZnO + Co system in the very low measurement (VSM) system.
concentration region ( y  0.01) has not been investigated.
We shall show that the behavior of Cu in this region is quite 3. Results and discussion
different and it acts only indirectly in affecting the moment
on the Co ions. In this paper, we present the changes The XRD data are given in figure 1 for Zn0.95−y Co0.05 Cu y O
in the magnetic moment in Co-doped ZnO due to small (0.00  y  0.0087) samples, annealed in the forming gas.
concentrations of Cu (0–0.87%) along with systematically The observed peaks, as marked on the figure, correspond to
introduced oxygen vacancies created by annealing in a the hexagonal wurtzite structure and no un-identified peaks
forming gas. were seen in any of the samples. The average particle size
for the Cu un-doped composition was estimated to be about
2. Experiment 22 nm from x-ray line broadening using the Scherrer formula
Dhkl = K λ/βhkl Cosθ , where Dhkl is the particle diameter in
Zn0.95−y Co0.05 Cu y O (0.00  y  0.0087) polycrystalline angstroms, K is the Scherer coefficient equal to 0.89, β is the
nanoparticles were synthesized by the chemical route reported full width at half maximum (FWHM), and λ is the wavelength
earlier [19]. Earlier we have reported in detail the of x-rays. (Slightly more broadening of the peaks is observed
ferromagnetic behavior of similarly prepared Zn1−x Cox O (x = in the Cu-doped samples and is understood to be due to the
0.02 to 0.10) [19, 20] nanoparticles and found that only additional strains due to the added dopant.)
the compositions up to x = 0.06 were monophase in our Due to the limited resolution of the XRD in identifying
preparation route. In view of this, we have kept the Co small traces of an impurity phase, in particular, the presence
concentration in the present samples at less than x = 0.06 of clusters of Co or Cu, or other impurity phases e.g. Co2 O3
while concentration of the co-doped (Cu) ions was varied or CoO, XPS measurements were performed which are known
between 0 and 0.87%. The low Cu composition ensured that to be much more sensitive to the presence of small traces of
we stayed well within the range of Cu solubility in ZnO that such phases. Furthermore, this measurement is also useful to
is about 1% for preparations via the chemical route. For investigate the bonding characteristics and individual oxidation
improving the crystallinity and to generate oxygen vacancies, state(s) of Co and Cu ions in the ZnO lattice, crucial in coming
all the as-prepared samples were annealed at 600 ◦ C in a to a conclusion about the origin of ferromagnetism in the
forming gas (95%Ar–5%H) of 99.9% purity. The role of the DMS systems. While the XPS measurements were carried
forming gas is to generate O vacancies due to the reducing out on all the compositions, the data for three representative
atmosphere, as detailed in the earlier papers [19, 20]. Different compositions, namely Zn0.95−y Co0.05 Cu y O ( y = 0.00, 0.0025
sets of samples were prepared having the same nominal and 0.0087) are shown in figure 2 for the Co 2P3/2 and Co
composition but with different levels of vacancy concentration 2P1/2 XPS spectral region. It is apparent that in addition to
by treating them for different periods (6, 8 and 10 h the two main peaks (2P3/2 and P1/2 ) each peak is accompanied
respectively) in the forming gas. To verify the single-phase by its satellite. The observed binding energy of the Co 2P3/2

2
J. Phys.: Condens. Matter 20 (2008) 255223 M Naeem et al

Figure 2. XPS spectra of Co 2p core levels of Zn0.95−y Co0.05 Cu y O

for different Cu concentrations ( y = 0.00, 0.0025, 0.0087).

Figure 4. (a) XPS spectra of Cu 2p core levels of

Zn0.95−y Co0.05 Cu y O (0  y  0.00875). Colored lines are the
Gaussian fitted curves; blue curve is for the LBEC and the green
curve for the HBEC peak (see text for details). (b) Relative areas
under the curves for the HBEC peaks obtained by the Gaussian fits to
the data of curves from figure 4 (a).

comparison purposes a cobalt metallic foil sample was also

studied. Data are shown in figure 3. It is clear that the Co edge
Figure 3. Co K-edge XANES spectra of Zn0.95−y Co0.05 Cu y O absorption for the metallic foil is at 7713 eV as expected from
nanoparticles. (Dotted line for y = 0.00; dashed line for y = 0.0013
and dash–dotted line for y = 0.005.) The spectrum for Co foil the literature [23, 24] while the Co edge for the samples lies
(solid line) is also given for comparison. at about 4 eV below this value consistent with the expectation
for Co in a +2 charge state [23, 24]. The pre-edge structure
in transition metals has been attributed to the 1s–3d transition,
peak is 781.5 eV, while that for the Co 2P1/2 is at 797 eV, while for the case of Co substituted in ZnO it is attributed to
with an energy difference of E = 15.5 eV between the two the transition from the 1s to the hybrid orbital (Co3d–O2p).
peaks. Comparing the observed spectra with those reported The lowered pre-edge structure is a signature [24] of Co in
for Co metal (778 eV for the Co 2p3/2 peak); with the the +2 state as opposed to the Co in the metallic state. With
energy difference of the two peaks for Co+2 in CoO (E = increasing Cu content the pre-edge peak becomes less well
15.05 eV), and with the absence of the satellite peaks of Co+3 defined, however, it remains distinct from the edge in metallic
in γ -Co2 O3 [21, 22], we can safely conclude that the electronic copper. The XANES data further confirms that Co is in a non-
state of Co in our samples is Co+2 and that it is not bonded zero oxidation state in our samples.
to oxygen as CoO or Co2 O3 . It also rules out metallic Co The XPS measurements were also used to study the oxida-
clusters in any of the samples, to our degree of resolution. We tion states of Cu ions (Cu+2 and Cu+1 ) in the (Zn, Co)O matrix.
therefore conclude that Co is present in our nanoparticles in the Because of the very low Cu concentration, we have taken XPS
+2 oxidation state in tetrahedral symmetry. measurements at high resolution with a slow rate to clearly de-
The x-ray absorption near edge (XANES) spectrum for tect the signature of Cu 2p core levels. It is well known that
some of these compositions was also investigated for the Co K- Cu+2 produces a strong Cu 2p satellite peak at a higher binding
edge with a view to further confirming the absence of metallic energy, presumably related to the presence of Cu 3d hole states.
cobalt in these systems. Measurements were carried out on These satellites have been attributed to the shake-up transitions
beamline number X23A2 of the National Synchrotron Light by ligand-to-metal 3d charge transfer. This charge transfer
Source (NSLS) at Brookhaven National Laboratory (BNL). cannot occur in Cu+1 compounds and metallic Cu because of
These studies were carried out on the samples with copper their completely filled 3d shells. Figure 4(a) shows high res-
concentrations of y = 0, 0.0013 and 0.005 respectively. For olution XPS spectra of Cu 2p core levels of all Cu co-doped

3
J. Phys.: Condens. Matter 20 (2008) 255223 M Naeem et al

Figure 5. (a) The typical XPS spectra of the O 1s core level recorded from the Zn0.9475 Co0.05 Cu0.0025 O nanoparticles; main (black curve) is the
data fit to a two-peak Gaussian. The two Gaussian peaks (HBEC and LBEC) obtained from the fit are shown in green. (b) Relative area of
HBEC curves obtained from the fits as in figure (a) for different Cu concentrations. A peak in the area is obvious for y = 0.0025
(see text for details).

(Zn, Co)O nanoparticles. In addition to this, XPS measure- the dominant one, as also observed in our case. It has been
ments were also performed on the samples with zero copper argued that the existence of Cu in a mixed ionic state is likely
concentration i.e. Zn0.95 Co0.05O in a similar energy range and to facilitate the presence of point defects [26] so as to retain
the data are shown for reference. The systematic broadening charge neutrality in the system. Since the oxygen vacancies
of the Cu 2p3/2 peak observed for increasing Cu concentration constitute the primary point defects in our system it is inter-
implies the presence of a multi-component peak of Cu which esting to determine whether any connection exists between the
can be de-convoluted into two peaks, labeled as ‘high binding two, namely the presence of Cu in the +1 state and the stabi-
energy component’ and ‘low binding energy component’, by lization of oxygen vacancies. This correlation was studied by
fitting with a two-peak Gaussian function. The high binding considering the XPS spectra of oxygen in our samples. In the
energy component (933.5 eV) and low binding energy com- inset of figure 5(a), we present a typical O 1s XPS spectrum of
ponent (932.2 eV) have been assigned to the Cu+2 and Cu+1 Zn0.9475Co0.05Cu0.0025O, which clearly showed an asymmetric
charge states as displayed in figure 4(a). In general, core level peak around 530 eV and with a shoulder at around 531.7 eV.
binding energy increases with increasing positive valence of The O 1s spectra can clearly be resolved into two compo-
the ion [25]. It is worth noticing that the peak of Cu 2p3/2 at nents. The LBEC can be ascribed to O−2 ions in a wurtzite
lower concentration (i.e. y = 0.0013, y = 0.0025) is almost structure of hexagonal Zn+2 ion arrays, while the HBEC is at-
symmetric (centered at 933.5 eV) and can be fitted by a single tributed in the literature to O−2 ions in the oxygen deficient
Gaussian function. However, with increasing Cu incorporation regions [27, 28]. All O 1s spectra were fitted by two symmetri-
the peak begins to widen systematically towards the lower en- cal peaks (named LBEC and HBEC) and the ratio of the num-
ergy side and becomes more asymmetric, particularly for the ber of O ions neighboring the defect sites to those in normal
Cu concentration y  0.005. Since the data could only be fit positions was obtained from the ratios of the areas under the
in this range of compositions with a two-peak fit, it suggests peak for the HBEC and LBEC peaks respectively. This ratio
that there is a mixed valence ionic state of Cu in the systems. is typically used to give a qualitative indication of the concen-
Attributing the high binding energy component (HBEC) and tration of vacancies in these systems [19, 29]. In figure 5(b)
low binding energy component (LBEC) peaks obtained from we show the plot of this ratio against the Cu concentration.
the fit to the Cu+2 and Cu+1 respectively, as discussed above, It is clear from this figure that while for low Cu concentra-
the ratio of Cu+1 /Cu+2 was estimated from the ratios of the tions (0  y  0.0025) the relative area increases strongly,
areas under the peak for the respective peaks. This ratio is at higher Cu concentrations ( y  0.0025) it decreases with in-
shown for different Cu concentrations in figure 4(b). It can be crease of Cu concentration. We interpret this as suggesting that
clearly seen that in the case of lower Cu concentration i.e. for the O vacancy concentration tends to increase strongly with in-
the case of y = 0.0013 and 0.0025, where the peak was lo- creasing Cu content for low Cu content, while it peaks and
cated almost symmetrically at E ∼ 933.5 eV, almost all Cu is begins to show a decrease for high enough Cu concentrations.
in the +2 ionic state. However, this ratio was observed to in- When seen in conjunction with the aforementioned Cu 2p
crease with further increase of Cu composition, suggesting that core spectra, it can be concluded that the concentration of
the number of Cu+1 ions increases more than those in the +2 oxygen vacancies increases with the increasing amount of Cu
state. This trend continues systematically with increasing Cu concentration in the range 0  y  0.0025, where almost all
content, suggesting that higher Cu concentration favors the de- the Cu ions are in the +2 ionic state. On the other hand the
velopment of the Cu+1 ionic state. Chakraborti et al [26] have O vacancy concentration begins to decrease when Cu begins to
studied a similar system and have concluded that Cu exists in enter in the +1 state as well. While no studies on the mutual
a mixed oxidation state of +1 and +2 [26] with Cu+2 being stability of Cu impurities and O vacancies in ZnO have come to

4
J. Phys.: Condens. Matter 20 (2008) 255223 M Naeem et al

Figure 6. (a) Magnetization ( M(H )) curves of Zn0.95−y Co0.05 Cu y O (0  y  0.0087) nanoparticles measured at 300 K. (b) Variation of Ms
(emu g−1 ) with Cu concentrations. The peak in the moment is apparent for y = 0.0025.

our notice, a computational study [30] of the combined effects of Co-doped ZnO and these have addressed the issue of the
of oxygen vacancies and Cu dopants in a similar wide band role of hole mediated ferromagnetism [31–33]. Hole mediated
gap doped semiconductor oxide, TiO2 , shows an interesting ferromagnetism has been shown in these systems and the
feature. It has been shown clearly that the presence of Cu role of O vacancies has been seen to be deleterious to the
impurities stabilizes the O vacancies and that the vacancies formation of the FM moment [34]. These aforementioned
tend to reside close to the impurities [30]. Therefore, in studies were conducted, however, in a much higher range
view of our own results we may argue that the stabilization of Cu concentrations (Cu 5–15%). Furthermore, the carrier
of oxygen vacancies occurs via the Cu in the +2 ionic state. concentration was shown to be drastically decreased on the
However, higher Cu concentration also appears to allow the addition of Cu and was also related to the role of Cu+1 as a
Cu +1 ionic state (in addition to the dominant +2 state) which deep level acceptor impurity or to Cu+2 as an electron trap.
correlates with the diminishing number of oxygen vacancies. We emphasize that our composition range (less than 1%) is
This clearly shows that Cu in the +2 ionic states supports the well below most of these studies and the strong increase of the
formation of O vacancies while in the +1 state it destabilizes moment with Cu addition (in Zn–CoO) and its absence in the
them. Why should Cu in the +1 state be unfavorable for the pure Zn–CuO nanoparticles reflects that Cu itself is definitely
stabilization of the O vacancies? We understand this issue at not developing a moment in this concentration range. The
least qualitatively as follows. The O vacancies create a region effect of Cu develops, as we shall substantiate later, indirectly,
of positive charge in their neighborhood and this tends to attract via its role in affecting the concentration of O vacancies.
and bind electrons (F-centers) thereby minimizing the system To illustrate this significant feature we consider the data of
energy. In the +1 state of Cu fewer electrons are being made figure 6(b) along with figures 4(b) and 5(b) where we show the
available (than in the +2 state) and the bare vacancies are made variation of the moment, the estimate of the Cu+1 /Cu+2 ratio
less stable as more and more of the Cu tends to go in the +1 and the estimate of oxygen vacancy concentration, as functions
state. of the Cu concentration. It is apparent from a consideration of
The magnetic properties of Cu co-doped (Zn, Co)O figures 5 and 6(b) that both the O vacancy concentration and
nanoparticles were investigated using a vibrating sample the moment rise steadily until y = 0.0025, while both features
magnetometer (VSM) system. The magnetization versus show a very similar decline beyond it. Thus the rapid increase
magnetic field ( M – H ) data nanoparticles, annealed in the in the moment in this range clearly seems to be correlated
forming gas, showed a typical ferromagnetic hysteresis loop. with the formation of a higher O vacancy concentration and its
All of the forming gas annealed samples showed ferromagnetic concomitant effects on the ferromagnetism via, for example,
behavior, as can be seen from figure 6(a). In contrast to the the ability to form magnetic polarons. To further strengthen
samples annealed in forming gas, the air annealed samples the hypothesis that the decrease of magnetization observed
showed non-magnetic behavior (data not shown here) down to beyond y = 0.0025 is a correlated effect of increasing Cu+1
10 K, the lowest measured temperature. Furthermore, in the ions and the destabilizing of oxygen vacancies, we performed
ZnO nanoparticles having only Cu as a dopant (Co=0%) no longer time anneals of the samples in the reducing atmosphere,
moment was observed in either air or A–H annealed samples, thereby generating more vacancies. The samples all had a
for these low Cu concentrations (Cu < 1%). The variation of fixed Co content of 4% and had variation of the Cu content
the magnetization with Cu content in the co-doped samples is in the same manner as described earlier. The samples were
shown in figure 6(b). It is noticeable that the moment varies in a annealed in the forming gas for different times, namely 6,
non-monotonic manner, peaking at y = 0.0025 and decreasing 8 and 10 h. One may expect, as discussed above, that the
steadily thereafter. It is noticeable that there is a very strong longer time annealed samples would have a higher O vacancy
increase in the moment, from 0.7 to 1.8 emu g−1 (0.25 to concentration. The data for the variation of the moment
0.47 μB /Co) in the initial region. There have been several with Cu content in these three sets of samples are shown in
studies on the effects of Cu addition on the magnetization figure 7. Interestingly we find that the position of the peak

5
J. Phys.: Condens. Matter 20 (2008) 255223 M Naeem et al

of Cu dopants in the initial range of concentration (up to the

observed maximum in moment) as enhancing this overlapping
by increasing the concentration of oxygen vacancies, leading
to a more effective F-center interaction which results in a
stronger FM behavior. The reduction of magnetization in the
system, with further increase of Cu dopants, appears to be
related to the increased tendency of Cu to go in as a Cu+1
ion, reducing the number of available carriers, and resulting
apparently in the destabilization of some of the oxygen
vacancies. In this (higher) range of Cu concentrations the
smaller number of oxygen vacancies that are present possibly
generate discontinuities in the exchange coupling between the
Figure 7. Ms versus Cu concentrations in Zn0.96−y Co0.04 Cu y O magnetic polarons, thereby weakening the FM and lowering
nanoparticles annealed for 6, 8 and 10 h respectively in the forming the observed moment.
gas at 600 ◦ C. (Squares: 6 h; circles: 8 h; up-triangles: 10 h.) Arrows In conclusion, we have shown that in the very low
indicate positions of the peaks for the indicated annealing times.
Dashed lines are a guide to the eye only. The shift in the position of
concentration region of Cu co-doping in a ferromagnetic Zn–
the peak in Ms to higher Cu concentrations with increased annealing Co O system, the role of Cu is initially to stabilize the
time is apparent. ferromagnetism via the generation of additional O vacancies
while at higher Cu content the number of vacancies is reduced
as soon as Cu starts to enter the system in a +1 ionic state.
in the moment shifts systematically to higher Cu content with Therefore, central to the magnetic behavior in our system is the
longer annealing times. For instance, the peak for the 6 h role of O vacancies in promoting ferromagnetism in Co-doped
annealed samples occurs at y = 0.005, while for the 8 h ZnO. We may safely conclude that any other defects or dopants
annealed samples it occurs at y = 0.0065 and finally for that are non-magnetic in themselves may indirectly affect the
the 10 h annealed samples it seems to be at y = 0.0075. magnetic behavior of the system if they affect the concentration
We interpret this shift in the peak position as illustrating the of the vacancies.
feature that when a larger concentration of O vacancies is
created, there are a large number of defects for mediating the Acknowledgments
ferromagnetism. It therefore requires a larger concentration of
the Cu to initiate a sufficient number of Cu+1 ions in the system SKH acknowledge support from the Higher Education
that may destabilize the O vacancy concentration sufficiently Commission of Pakistan Project ‘Development and Study of
for the moment to start decreasing. Magnetic Nanostructures’. The authors acknowledge the help
Hence the development of the ferromagnetic moment in of Dr J Woicik from the National Institute of Standards and
the Cu co-doped system in our range of concentrations is a Technology USA for performing the XANES measurements.
competition between the role of O vacancies in promoting
ferromagnetism and the role of Cu as Cu+1 in destabilizing the
vacancy and hence weakening the ferromagnetism. Therefore References
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