See

discussions, stats, and author profiles for this publication at: http://www.researchgate.net/publication/278329290

Role of multivalent Cu, oxygen vacancies and

CuO nanophase in ferromagnetic properties of
ZnO:Cu thin films
ARTICLE in RSC ADVANCES JUNE 2015
Impact Factor: 3.71

DOWNLOADS

VIEWS

18

8 AUTHORS, INCLUDING:
Muhammad Younas

Fahad Azad

The University of Hong Kong

The University of Hong Kong

13 PUBLICATIONS 72 CITATIONS

2 PUBLICATIONS 0 CITATIONS

SEE PROFILE

SEE PROFILE

Muhammad Javed Akhtar

Asghari Maqsood

Pakistani Institute of Nuclear Science and T

Air University of Islamabad

85 PUBLICATIONS 627 CITATIONS

172 PUBLICATIONS 1,263 CITATIONS

SEE PROFILE

SEE PROFILE

Available from: Asghari Maqsood

Retrieved on: 23 June 2015

RSC Advances

c5ra09002d

PAPER

Role of multivalent Cu, oxygen vacancies and CuO

nanophase in the ferromagnetic properties of
ZnO:Cu thin lms
M. Younas,* Junying Shen, Mingquan He, R. Lortz,
Fahad Azad, M. J. Akhtar, A. Maqsood and F. C. C. Ling*

10

15

20

25

30

Comprehensive microstructural, electronic and magnetic

analyses have been carried out on ZnO:Cu thin lms grown
by pulsed laser deposition on c-plane sapphire under
dierent oxygen partial pressures. Detailed X-ray diraction
(XRD), X-ray photoelectron spectroscopy (XPS) and high
resolution transmission electron microscopy (HRTEM)
analyses reveal that increase in oxygen growth pressure
degrades the epitaxy of ZnO:Cu thin lms due to inclusion of
nanosize CuO in the ZnO host lattice. HRTEM and
Please check this
proofsuggest
carefully.
not read
magnetization
studies
thatOur
thinstaff
lmwill
quality
playsitain detail after you have submitted your proof corrections.
less eective role in governing the magnetic properties of
Translation
errors
between
les and typesetting systems can occur so the whole proof needs to be read.
these
samples.
Instead,
roomword-processor
temperature ferromagnetism
Please
particular
to: tabulated
material;
equations;
numerical data; gures and graphics; and references. If you
(FM)
of pay
these
ZnO:Cuattention
thin lm samples
are highly
tunable
by
the
presence the
of CuO
nanophasesauthor(s)
and
havesimultaneous
not already indicated
corresponding
please mark their name(s) with an asterisk. Corrections at this stage
multivalent
Cu and
V$$
concentrations,
which
are in strong
should be minor
and
involve extensive
changes.
Please do not directly edit the text within the PDF le or send a revised
Onot
contest
with
each
other.
Formust
low be
oxygen
partialatpressure
manuscript. All corrections
submitted
the
same time.
1
grown sample, the eective Cu2  V$$
network is the
O  Cu
main
to the
FM and
is in completion
Pleasecontributor
minor layout
improvements,
e.g. in line breaking, table widths and graphic placement, are routinely
bear in mind
thatobserved
with CuO nanophases only when there is a relatively low V$$
O
applied to the nal version.
2+
concentration with a dominant Cu oxidation state. For
$$
vacuum grown samples containing high VO concentration
1 receiving your corrections; no late corrections will be made.
We will
publish
articlesoxidation
on the web
as soon
as2possible
after
and
Cu1+
as dominant
state,
the Cu
 V$$
O  Cu
network becomes less eective and a CuO nanophase (45
where
possible
Please
return
your nal
nm)
is the
dominent
FMcorrections,
supplier. The
extrinsic
FM inwithin
the 48 hours of receipt following the instructions in the proof notication email.
vacuum
grown sample, which is the best epitaxial quality
sample, is further conrmed by the zero eld cooled (ZFC)
and eld cooled (FC) magnetization protocols.

10

15

20

25

30

35

35

40

40

45

45

50

50

ART
C5RA09002D_GRABS

Queries for the attention of the authors

Journal: RSC Advances

5

Paper: c5ra09002d
Title: Role of multivalent Cu, oxygen vacancies and CuO nanophase in the ferromagnetic properties of ZnO:Cu
thin films

10

Editor's queries are marked like this... 1 , and for your convenience line numbers are inserted like this... 5

10

Please ensure that all queries are answered when returning your proof corrections so that publication of your
article is not delayed.
15

Query
Reference

Query

For your information: You can cite this article before you receive
notication of the page numbers by using the following format:
(authors), RSC Adv., (year), DOI: 10.1039/c5ra09002d.

Please carefully check the spelling of all author names. This is

important for the correct indexing and future citation of your
article. No late corrections can be made.

Do you wish to add an e-mail address for the corresponding

author?

The graphical abstract text currently exceeds the space available

for the published version. Please trim the text so that it is less than
250 characters (including spaces).

Ref. 1 and 40: Please provide the initial(s) for the 1st author.

Ref. 3: Please provide the initial(s) for the 4th author.

Ref. 4: Please provide the last name for the 7th author.

20

25

30

Remarks

15

20

25

30

35

35

40

40

45

45

50

50

55

55

ART
C5RA09002D_GRABS

RSC Advances
PAPER
1
1

Cite this: DOI: 10.1039/c5ra09002d

Role of multivalent Cu, oxygen vacancies and CuO

nanophase in the ferromagnetic properties of
ZnO:Cu thin lms

M. Younas,*a Junying Shen,b Mingquan He,b R. Lortz,b Fahad Azad,ac M. J. Akhtar,d

A. Maqsoode and F. C. C. Ling*a

10

Comprehensive microstructural, electronic and magnetic analyses have been carried out on ZnO:Cu thin
lms grown by pulsed laser deposition on c-plane sapphire under dierent oxygen partial pressures.

10

Detailed X-ray diraction (XRD), X-ray photoelectron spectroscopy (XPS) and high resolution
transmission electron microscopy (HRTEM) analyses reveal that increase in oxygen growth pressure
degrades the epitaxy of ZnO:Cu thin lms due to inclusion of nanosize CuO in the ZnO host lattice.

15

HRTEM and magnetization studies suggest that thin lm quality plays a less eective role in governing

15

the magnetic properties of these samples. Instead, room temperature ferromagnetism (FM) of these
ZnO:Cu thin lm samples are highly tunable by the simultaneous presence of CuO nanophases and
multivalent Cu and V$$
O concentrations, which are in strong contest with each other. For low oxygen

1
network is the main contributor to the
partial pressure grown sample, the eective Cu2  V$$
O  Cu

20
Received 14th May 2015
Accepted 15th June 2015

observed FM and is in completion with CuO nanophases only when there is a relatively low V$$
O
concentration with a dominant Cu2+ oxidation state. For vacuum grown samples containing high V$$
O

20

1
concentration and Cu1+ as dominant oxidation state, the Cu2  V$$
network becomes less
O  Cu

eective and a CuO nanophase (45 nm) is the dominent FM supplier. The extrinsic FM in the vacuum

25

DOI: 10.1039/c5ra09002d

grown sample, which is the best epitaxial quality sample, is further conrmed by the zero eld cooled

www.rsc.org/advances

(ZFC) and eld cooled (FC) magnetization protocols.

1. Introduction
30

35

40

The control over the distribution of magnetic ions in a semiconducting host is crucial for the functionality of diluted
magnetic semiconductors (DMS). It is one of the major challenges to avoid secondary phases and precipitates due to the
clustering tendency of transition metal (TM) elements and their
oxides. Under nonequilibrium growth conditions, a strong
attractive interaction between TM impurities stimulates the
spinodal decomposition of magnetically robust nanocrystals.
Therefore, chemical phase separation in TM doped wide band
gap semiconductors such that GaN and ZnO is signicantly
anticipated.15 ZnO is an encouraging wide band gap semiconductor having ability to laser spontaneously at ultraviolet
wavelengths. Because of its long spin-coherence time at room

45
a

Department of Physics, The University of Hong Kong, Pokfulam Road, Hong Kong, P.
3 R. China
b

Department of Physics, Hong Kong University of Science and Technology, Clear Water
Bay, Kowloon, Hong Kong, P. R. China

50

c
School of Natural Sciences, National University of Sciences and Technology, H-12,
Islamabad, Pakistan
d

EMMG, Physics Division, PINSTECH, P.O. Nilore, Islamabad, Pakistan

Department of Physics, Air University, E-9 PAF Complex, Islamabad, Pakistan

This journal is The Royal Society of Chemistry 2015

temperature (RT), ZnO would possibly behave as a bipolar

spintronic material with the ferromagnetism (FM) mediated by
both holes and electrons.68 Although extensive research has
been conducted in order to nd a true ZnO-based DMS with
high Curie temperature (TC), controlled FM with its realistic
origin in ZnO based DMS911 is debatably one of the stimulating
research topic in materials science and condensed-matter
physics in these days. There are still open questions that challenge our understanding, such as whether the ferromagnetic
ordering arises from strong magnetic interactions between wellseparated magnetic dopants actually substituting at the host
lattice or from the magnetic secondary phases and metal
precipitates.
A possible way to avoid magnetic secondary phases or metal
precipitates is the doping of nonmagnetic elements, such as
Cu.12 One of such examples is the ZnO:Cu system as metallic
zinc, ZnO, metallic copper, Cu2O, and bulk CuO are not ferromagnetic.13 In addition, the size mismatch between Cu and Zn
is very small, resulting in a low formation energy for CuZn and a
small lattice distortion. Therefore, the ZnO:Cu system has been
predicted to be ferromagnetic and so it develops as one of the
major challenges to build a room temperature (RT) DMS using
nonmagnetic dopants. A substantial amount of experimental
data have already been collected, however there are some

RSC Adv., 2015, xx, 110 | 1

25

30

35

40

45

50

RSC Advances

10

15

20

25

30

35

40

45

50

55

controversies regarding true carrier mediated FM in this class of

materials.
One possible doubt on the DMS nature of the ZnO:Cu might
be the mixed valence state of the Cu in the ZnO materials. The
ZnO:Cu system containing CuZn+ (i.e., Cu3+) or CuZn0 (i.e., Cu2+)
is found to possess magnetic moments of 2 mB/Cu and 1 mB/Cu,
respectively. However, CuZn (Cu1+) or CuZn2 (i.e., Cu0) in
n-type samples would not possess any local magnetic moments
as the d electrons are fully lled. Under O-rich conditions
during sample growth, substituting Cu has the lowest formation energy and most of the Cu would be in the oxidation state
of +2 or +1 in the Cu:ZnO sample as EF is pinned around Cu2+/
Cu1+ conditions.14,15 Under O-poor conditions, the role of isolated oxygen vacancies V$$
O and zinc interstitials (Zni) are still
controversial in the ferromagnetic stability of the ZnO:Cu
system.16,17 However, donoracceptor defect pairs (DAPs) in
19
$$ 18
which Cu coupled to V$$
O or Zni such as Cu  V O , and CuZni
encourage the most interest because the overlap between
delocalized molecular orbitals can play a signicant role on the
development of ferromagnetic ordering in the ZnO:Cu system.
Another, most critical and important issue with DMS nature of
the ZnO:Cu is the formation of CuO nanophases that may
exhibit a ferromagnetic nature.20,21 However, in these reports
the magnetization of the ZnO:Cu system is solely tuned by the
presence of CuO inclusions, and the eect of multivalent Cu
and V$$
O on the magnetic behaviour is totally ignored. Moreover,
some researchers found that Cu related phases cannot regulate
magnetic properties of the ZnO:Cu system, since there is hardly
any interaction between Cu clusters and host lattice, which is
essential for a coupling to arise and clustering is revealed to be
detrimental to the FM.2224
In the above discussed scenario it is still unclear whether the
ferromagnetism originates from diluted spins of Cu elements or
results from secondary phase segregation or Cu metal clustering in the ZnO:Cu system. Therefore, in this research work,
we performed a comprehensive structural, electronic and
magnetic analysis on pulsed laser deposition (PLD) grown
ZnO:Cu thin lms to explore the possible Cu valence states,
defect complexes and potential role of secondary phases in
tuning the FM. To control Cu valence states and V$$
O concentrations, the ZnO:Cu thin lms were grown under dierent
oxygen partial pressures. Our nding shows that the CuO
nanophases alone cannot generate high magnetization as
previously thought.20,21 Instead, a mixed Cu oxidation state
coupled with oxygen vacancies V$$
O and CuO nanophases are
simultaneously playing a vital role to tune the magnetic properties. We suggest that RT FM in ZnO:Cu is not of single origin,
even when CuO secondary phases are present, and other
possible sources that can contribute should also be considered
in parallel.

2.

Experimental

The ZnO:Cu (with Cu0.04Zn0.96O stoichiometric composition of

the target with 99.999% purity) thin lms were grown on c-plane
sapphire substrate using a pulsed KrF excimer laser (l 248
nm) with a frequency of 2 Hz and energy of 300 mJ. Thin lm

2 | RSC Adv., 2015, xx, 110

Paper

growth was carried out in three dierent oxygen pressures,

namely PO2 0.00 Pa (S-1), 0.02 Pa (S-2) and 1.00 Pa (S-3) with
substrate temperature of 600  C. Thin lms samples used in the
present study had thickness in the range of 185280 nm. The
room temperature (RT) Hall Eect measurement was conducted
in a van der Pauw conguration (Accenet HL-5500 PC system).
Room-temperature X-ray diraction (XRD) measurements were
performed on a Siemens D5000 diractometer with the CuKa
line (0.1541 nm) to examine the structural properties. The
secondary ion mass spectroscopy (SIMS) measurement was
conducted using the Cameca (Model IMS 4F) dynamic
secondary ion mass spectrometer. The electronic structures
were studied by X-ray photoelectron spectroscopy (XPS) using
the MgKa line (Kratos Axis Ultra DLS system). The morphology
of the samples was studied by high resolution transmission
electron microscopy (HRTEM) (2010F TEM, JEOL). Magnetic
measurements were performed using a VSM SQUID magnetometer (MPMS-5s, Quantum Design). RT magnetic hysteresis
loops over 0.5 T have been recorded while magnetoresistance
(MR) measurements were carried out from 300 K to 1.5 K under
magnetic eld of 10 T. The zero-eld cooled (ZFC) and eldcooled (FC) magnetization vs. temperature studies were
performed from 1.5350 K under 100 Oe magnetic elds
perpendicular to the sample surface.

3.
3.1

10

15

20

25

Results and discussion

Structural and electronic properties

Sample S-1 is n-type (carrier concentration 3.32  1018 cm3)

while samples S-2 and S-3 do not have sucient conductivity for
assessing electrical parameters by Hall measurements and
show insulating behaviour (resistivity 108 U cm by IV
measurements). The XRD patterns for ZnO:Cu thin lms represented in Fig. 1(a) shows dominant reection from (002) and
(004) planes of wurtzite ZnO, and (006) planes of sapphire
substrate for all three samples. The (002) peak values of the
three samples are at 34.34 (S-1), 34.46 (S-2) and 34.49 (S-3)
with corresponding FWHM values of 0.23 , 0.24 and 0.28 ,
respectively. The (002) peak for the ZnO:Cu samples is at lower
positions than those of pristine ZnO thin lms grown under the
same conditions i.e. 34.491 , 34.540 and 34.568 for 0.00 Pa,
0.02 Pa and 1.00 Pa, respectively (shown by  marks in
Fig. 1(a)). From (002) peak positions, we estimated the c-axis
(S-1), 5.202 A
(S-2), 5.198 A

lattice parameter values of 5.220 A

(S-3) by employing the reduced Bragg relation c l/sin q, where
l is the X-ray wavelength and q is the diraction angel of (002)
peak.24 The c-axis lattice parameters for ZnO:Cu thin lms have
5.188
higher values than that of pristine ZnO thin lms (5.199 A,
and 5.186 A,
respectively for 0.00 Pa, 0.02 Pa and 1.00 Pa
A
grown samples). In view of the relevant ionic radii of Cu+(0.60
Cu2+(0.59 A)
and Zn2+(0.74 A),
25 the (002) peak positions of
A),
the ZnO:Cu system should shi towards higher angles with
linear decrease in c-parameters at lower Cu concentrations20
compared to pristine ZnO thin lms. However, we observe shi
in (002) peak positions towards lower angles and slightly higher
values of c-lattice parameters of the ZnO:Cu samples compared
to pristine ZnO thin lms. This abnormal trend stipulates the

This journal is The Royal Society of Chemistry 2015

30

35

40

45

50

55

Paper

10

15

20

25

30

35

40

45

50

55

possible evaluation of microstructural disorder and secondary

phase inclusions in the ZnO matrix that cause an expansion in
the host lattice without altering the overall wurtzite crystal
structure. On comparing the normalized intensities (inset
Fig. 1(a)), we observe an 81% reduction in (002) peak intensity
for the S-3 sample (grown in 1.00 Pa), compared to that of S-1
(grown in 0.00 Pa). Moreover, a maximum shi in the (002)
peak position with highest value of FWHM for S-3 sample is also
noticed. Since the epitaxial and structure quality of the sample
has positive relations to the intensity, sharpness and position of
the (002) peak in XRD spectrum, the preliminary XRD observations show that increasing oxygen partial pressures during
growth would degrade the epitaxial and structural quality of the
thin lm samples. Therefore, the relatively reduced intensity
and highest value of FHWM of the (002) peak for the S-3 sample
compared to the S-1 and S-2 samples are suggested to be due to
poor epitaxial and crystalline quality.
Along with the dominant peaks, we also observe two extra
peaks at 36 and 65 in the S-2 (PO2 0.02 Pa) sample, but
no such peaks are found in the S-1 and S-3 samples within the
detection limit of XRD. The observed peaks at 36 and 65 in
11) at 35.5
this case are very close to the reections from (1

and (022) at 65.7 planes of CuO (JCPDS#720629).26 Prior to
assigning these peaks to CuO secondary phases, we carried out
post-growth annealing on the S-1, S-2 and S-3 samples at 750  C
in Ar for 30 min. Aer Ar annealing, we again observe these
extra peaks at same positions (at 36 and 65 ) only in the
oxygen grown samples (S-2 and S-3), but no such peaks are
observed in the vacuum grown sample (S-1) when annealed
under the same conditions (Fig. 1(b)). This infers the possible
role of the oxygen supply during the thin lm growth in forming
CuO secondary phase. This may be due to the fact, that the host
crystalline ZnO structure would be interrupted by those inserted
secondary phases and we observed degraded intensities of (002)
peak with increasing PO2 (i.e. for S-2 and S-3 samples). Therefore, in the S-2 sample, we associate the peaks at 36 and 65
11) and (022) planes of CuO, respectively.
to reections from (1
Within the detection limit of the XRD we are unable to detect
CuO related peaks in vacuum (S-1) and high oxygen partial
pressure grown (S-3) samples. Relatively larger c-parameters for
these samples compared to pristine ZnO thin lms demand
additional deep analysis to completely rule out the existence of
CuO phases in S-1 and S-3 samples.
To further explore the Cu related secondary phases in the S1, S-2 and S-3 samples, we performed an XPS study. It is normally agreed that XPS can dierentiate between Cu metal, Cu2O
and CuO.27 Therefore, the Cu valence states are obtained from
the high resolution Cu-2p core level XPS spectra shown in Fig. 2.
For all the three samples, the respective Cu-2p3/2 and Cu-2p1/2
peak positions lying in the range of 932.8933.2 and 952.6
953.5 eV show the presence of the mixed Cu valence states,
which is in agreement with literature.28,29 Therefore, each XPS
spectrum is deconvolved into two components of Cu2+ and Cu1+
by Gaussian curve tting. The ttings are accomplished by
employing a Cu2+ component (by xing Cu-2p3/2 peak at 933.6
eV and Cu-2p1/2 peak at 953.5 eV corresponding to the peak
positions of Cu2+ in CuO) and a Cu1+ component (by xing
This journal is The Royal Society of Chemistry 2015

RSC Advances

10

15

20

25

30

35

Fig. 1 (a) XRD patterns for all three as-grown samples of ZnO:Cu thin
lms. The inset shows normalized (002) peak intensity. The  marks
shows (002) peak positions for all three pristine ZnO samples grown
under same conditions, and (b) XRD patterns after annealing all three
ZnO:Cu samples at 750  C. Secondary phase peaks are represented by
black squares.

40

45
Cu-2p3/2 peak at 932.6 eV and Cu-2p1/2 peak at 952.5 eV corresponding to the peak positions of Cu1+ in Cu2O),26 and the
tting results are presented in Table 1. By employing XPS
integrated areas and Cu-2p3/2/Zn-2p3/2 ratio aer proper
normalization of corresponding atomic sensitivity factor, we
estimated the Cu at.% of 2.31, 2.57 and 1.55 for the S-1, S-2 and
S-3 samples, respectively. For S-1 sample, the relative peak
intensity for Cu1+-2p3/2 compared to Cu2+-2p3/2 is high, without
any satellite structure. Strong satellite peaks due to electron
shakeup are commonly found between 940 eV and 945 eV for
Cu2+ (Cu-3d9)18 and no satellites are expected for Cu0 and Cu1+.
The S-1 sample with relatively high Cu1+-2p3/2 peak intensity
and absence of a satellite structure suggest the presence of Cu1+

RSC Adv., 2015, xx, 110 | 3

50

55

RSC Advances

Paper

10

15

20

25

30

35

40

45

Fig. 2 Cu-2p XPS spectrum for S-1 sample. The left and right insets
show Cu-2p XPS spectra for S-2 & S-3 samples, respectively.

as more dominant oxidation state compared to Cu2+. Since S-1

sample is grown in oxygen free environment that may
contains higher Cu1+/Cu2+ ratio thereby suppressing the satellite structure in the XPS spectra. Therefore, the Cu1+ as more
dominant oxidation state and its fully lled 3d orbitals (3d104s0)
may be one of the possible reasons for the absence of CuO
secondary phases in XRD and Cu-XPS results of S-1 sample, as
discussed previously. However, samples grown in oxygen partial
pressures (S-2 and S-3) show two clear satellite peaks (Fig. 2 le
& right insets) with binding energies (BE) in the range of 940
943 eV and 961963 eV, indicating the presence of Cu2+ at the
tetrahedral zinc site.28,30 The dominant divalent state of the Cu
ions results from the strong CuO bonding in CuO4 tetrahedron, which can suppresses the Cu solubility in ZnO and may
lead to the CuO formation.31 The CuO phase is normally characterized by high-intensity shake-up satellites at higher BE (10
eV) than that of main Cu-2p3/2 and Cu-2p1/2 peaks, which are
considerably broader than that of bulk Cu2O and Cu
metal.30,32,33 Observation of satellite peak positions 8.3110.31
eV above the main Cu-2p peaks in S-2 and S-3 samples clearly
points towards possible CuO secondary phases in these
samples.
In order to see the eects of V$$
O on the bonding nature of
oxygen with Cu sitting at Zn site, we performed O-1s XPS
measurements shown in Fig. 3. The O-1s XPS peaks for all

samples are tted using three Gaussian curve ttings. The

asymmetric features observed in O-1s spectra are deconvolved
by several subspectral components: (i) the OL (530.50  0.10 eV)
peak shows typical behaviour of O2 ions arranged in a wurtzite
lattice of hexagonal Zn2+ ions (ii) the V$$
O (531.30  0.20 eV) peak
indicating oxygen decient regions within defective ZnO:Cu
matrix with intensity directly related to V$$
O concentration and
(iii) the OS (532.10  0.20 eV) peak normally associated to the
loosely bound adsorbed oxygen at the surface or oxygen interstitial.34 The V$$
O (531.10  0.20 eV) peak intensity gradually
decreases (Fig. 3) with increasing oxygen pressure during
growth. This indicates relatively higher V$$
O concentrations in
sample S-1 compared to other samples, in agreement with the
Cu-2p XPS spectra where we observed Cu1+ as more dominant
oxidation state for the same sample. The OS (532.10  0.20 eV)
peak more or less has same intensity for S-2 and S-3 samples
showing that oxygen supply during growth of these samples
enhances the surface oxidation (Fig. 3 le and right insets)
when compared to S-1 (vacuum grown sample). These XPS
results reveal an enhanced surface oxidation of Cu species
during oxygen growth compared to vacuum growth conditions.
One of the intuitive reasons accounting for the observation is
that more and more oxygen molecules are available for
oxidizing Cu that can form larger size CuO phases for S-2 and

10

15

20

25

30

35

40

45

Fig. 3 O-1s XPS spectra for S-1 sample. The left and right insets show
O-1s XPS spectra for S-2 & S-3 samples, respectively.

50

50
Table 1

55

S-1
S-2
S-3
a

XPS tting parameters for all three thin lm samples

Cu-2p3/2 (eV)

FWHM (eV)

Cu-2p1/2 (eV)

FWHM (eV)

SP-1a (eV)

SP-2a (eV)

933.02  0.02
933.16  0.02
932.83  0.01

1.33
1.88
1.77

952.81  0.05
952.93  0.05
952.72  0.03

1.49
2.09
2.14

943.47  0.3
940.88  0.3

963.00  0.4
961.03  0.2

SP stands for satellite peak.

4 | RSC Adv., 2015, xx, 110

This journal is The Royal Society of Chemistry 2015

55

Paper

S-3 samples in agreement with XRD results discussed

previously.
3.2

10

15

20

25

30

35

Microstructural properties

XPS results for S-2 and S-3 samples show a possible presence of
CuO phases, but discard their presence in the S-1 sample. XPS is
a surface sensitive technique and has some detection limit
problems. Moreover, the S-1 sample is grown in vacuum, which
is not a favourable condition for the growth of large and stable
CuO secondary phases. The CuO nanophases that are very small
in size, present either at the surface or within the bulk of the
host material, might remain undetected by XPS. Therefore, in
order to investigate the defect structure, phase segregation and
Cu related secondary phases; we performed a detailed HRTEM
analysis on all three as grown samples. Fig. 4 shows a crosssectional HRTEM image at the lmsubstrate interface for the
S-1 sample. The HRTEM image in Fig. 4 shows a perfect ZnO
growth along the (002) plane and the interface is atomically
sharp. The diraction pattern from the lmsubstrate interface
(inset Fig. 4) shows absence of spots apart from those belonging
to the lm and substrate. The native ZnO:Cu lm in this
micrograph shows some image contrast in the form of a lattice
distortion (white circle in Fig. 4). By employing HRTEM, Klenov
et al.35 reported that CuO planar clusters (with cluster concentrations more than 2 atom%) can be incorporated in (001)
cationic planes of ZnO at Zn atom positions, with oxygen atoms
situated in the adjacent anion planes resulting in the appearance of a dislocation loop. Moreover Zn and Cu atoms are
almost equal to each other in their scattering properties, so the
substitution of Cu for Zn does not aect the image contrast, and
the associated oxygen lattice distortion provides additional
contrast in the HRTEM images. XPS and XRD results did not
reveal any Cu clustering, and the Cu atomic concentrations is
also higher than 2 atom% for S-1 sample (i.e. 2.3 atom%).

RSC Advances

Hence, the observed defects along the (001) planes (white circle
in Fig. 4) are likely to be of a dislocation nature in the S-1
sample.
To further conrm the origin of these dislocations, we
carried out a low magnication TEM analysis of native ZnO:Cu
thin lm of S-1 sample as shown in Fig. 5. The micrograph in
this gure reveals randomly dispersed Moire fringes, as seen by
the bending/wrinkling of the lattice fringes (white circle in
Fig. 5) with average size in 34 nm range. Moire fringes normally appear between two crystal structures with parallel or
rotated sets of planes.36 The high magnication image presented in the le inset of Fig. 5 shows a lattice distortion caused
by such a Moire fringe. This lattice distortion is primarily
caused by lattice mismatch between the host material (ZnO:Cu)
and CuO secondary phase. The estimated interplanar distance
from such a distorted lattice is 0.25 nm, which corresponds to
11) planes of monoclinic CuO
the reection from (1
(JCPDS#720629). Furthermore, the interplanar distance of
0.26 nm corresponds to the (002) planes of wurtzite ZnO. This is
in good agreement with XRD results of the S-1 sample where the
(002) plane is dominant in the ZnO:Cu lms. A very small
dierence (0.01 nm) between the interplanar distances of the
distorted lattice and the undistorted wurtzite ZnO indicates the
11) planes of CuO to the (002)
parallel overlapping of the (1
planes of wurtzite ZnO. This is further conrmed by the electron
diraction pattern (right inset of Fig. 5), for which we are unable
to observe separate diraction spots for the CuO secondary
phase. Instead, relatively elongated diraction spots are seen
here, probably due to a very small dierence in the interplanar
11) planes of CuO to the (002)
distances of the overlapping (1
planes of wurtzite ZnO. Thus, some of the Cu atoms alloyed with
ZnO exist as planar nanophases of CuO (34 nm), intermingled

10

15

20

25

30

35

40

40

45

45

50

50

55

55
Cross-sectional HRTEM image at the lmsubstrate interface
for S-1 sample. The inset shows an electron diraction pattern from
the lmsubstrate interface of the same sample.
Fig. 4

This journal is The Royal Society of Chemistry 2015

Fig. 5 Low magnication image for the S-1 sample. The left inset
shows an HRTEM image of the selected Moire fringes. The right inset
shows an electron diraction pattern from the native ZnO:Cu lm of
sample S-1.

RSC Adv., 2015, xx, 110 | 5

RSC Advances

10

15

20

25

30

35

with the (001) cationic planes of ZnO resulting in the observed

dislocation loop.
Sample S-2 and S-3 grown under oxygen partial pressures
show dierent results in the TEM analysis. In the low magnication image of the S-2 sample presented in Fig. 6, we can still
observe some image contrasts and Moire's fringes in the form of
wrinkling of the lattice (indicated by the white circle). In the
HRTEM image (le inset of Fig. 6) of the S-2 sample, a sharp and
parallel arrangement of lattice fringes can be seen very close to
the interface. However, away from lmsubstrate interface, a
deviation from epitaxial growth can also be observed in the
form of un-patterned lattice fringes. Moreover, similar to the S-1
sample, dislocation loops of 56 nm size (indicated by white
circles) are also noticed for the S-2 sample. The electron
diraction pattern from the lmsubstrate interface of the S-2
sample (right inset of Fig. 6) shows epitaxial growth of the
(002) plane. However, the diraction spots are not sharp
enough as observed for the S-1 sample and some very dull extra
spots (white arrows in le inset of Fig. 6) are also found. Since
the atomic weights of CuO and ZnO are very close to each other,
it is relatively dicult to observe separate clear diraction spots
for CuO if these phases are of very small size and present along
the ZnO growth planes, as discussed earlier.
Therefore, extra spots observed in the electron diraction
pattern of S-2 samples are signatures for CuO secondary phases
as normally interpreted in the literature.32 However; the other
important point regarding extra spots that appeared in electron
diraction pattern of the S-2 sample is their potential link to the
deviation from epitaxial growth of thin lm. The extra spots
detected in the electron diraction pattern are normally linked
to only Cu related secondary phases and information on the
epitaxial quality of lm is not available, even when multiple
peaks appeared in the XRD pattern of the ZnO:Cu thin lm.32
The possible increase in number and size of these inserted CuO

40

45

50

55
Fig. 6 Low magnication image for the S-2 sample. The left inset
shows an HRTEM image at the lmsubstrate interface for the same
sample. The right inset shows an electron diraction pattern from the
lmsubstrate interface of sample S-2.

6 | RSC Adv., 2015, xx, 110

Paper

nanophases would interrupt the crystalline host ZnO structure.

Therefore the extra spots related to CuO in the electron
diraction pattern demonstrate a deviation from epitaxial
growth for the S-2 sample. The lower epitaxial quality for this
sample is also evident by reduced (002) peak intensity with
increased FWHM compared to S-1 sample in XRD results discussed earlier.
However, high oxygen partial pressure during growth (S-3
sample) seems to drastically change the epitaxial quality of the
lm as seen by the columnar structure of native ZnO:Cu in the
low magnication TEM image (Fig. 7). These observed columnar
structures might be related to the conversion of epitaxial regions
to polycrystalline regions due to localized epitaxial disorder. The
HRTEM image taken from the lmsubstrate interface (le inset
of Fig. 7) reveals un-patterned and intermingled lattice fringes
that appeared to be amorphous regions in direct vicinity to the
interface (indicated by white brackets). To investigate the presence of any type of clustering at the lmsubstrate interface that
may cause these amorphous regions, we performed SIMS on S-3
sample. The SIMS results for sample S-3 shown in Fig. 8
demonstrate uniform depth proles of Zn, Al, O and Cu
elements. Cu doping seems to be uniformly distributed without
any type of Cu clustering at the lmsubstrate interface.
Therefore, these intermingled lattice fringes are associated with
dislocation loops caused by inclusion of CuO nanophases. High
oxygen pressure during growth facilitates small sized CuO to
cluster into larger sized CuO (810 nm) nanophases that would
spread throughout the host lattice at the expense of localized
epitaxial disorder. Apart from the lmsubstrate interface
region, we can still see parallel lattice fringes at the native
ZnO:Cu lm and deviation from epitaxial order is only restricted
to some localized regions, while the overall lm structure
maintains its epitaxial growth. The localized level polycrystallinity of S-3 can also be seen from multiple spots that
appear in the electron diraction pattern from the lm
substrate interface (right inset of Fig. 7). Although the oxygen
supply during growth lowers the epitaxial quality of ZnO:Cu thin
lms, the S-2 and S-3 samples did not fully convert to polycrystalline thin lms and we observe only localized level epitaxial
disorder. These samples still show epitaxial thin lm growth in
agreement with the XRD results where we observed dominant
reection from (002) and (004) planes indicating wurtzite
structure with its c axis orientation normal to the surface.
From XRD, XPS and TEM observations, we establish a relation among oxygen partial pressure during growth, evolution of
CuO nanophases and epitaxial quality of thin lm samples.
Introduction of oxygen during growth of ZnO:Cu thin lms
enhances the CuO nanophase formation and the nanophase
inclusion aects epitaxy and crystal quality of the thin lm.
However, thin lm growth without oxygen shows perfect epitaxy
with much better crystalline quality and even small size CuO
nanophases interspersed along the (001) plane of the host ZnO
has no eect on the crystal quality compared to the S-2 and S-3
samples. XPS is a surface sensitive technique shows CuO
secondary phases only for S-2 and S-3 samples, but TEM analysis shows existence of CuO nanophases in the matrix of ZnO
even close to the lmsubstrate interface for the S-1, S-2 and S-3

This journal is The Royal Society of Chemistry 2015

10

15

20

25

30

35

40

45

50

55

Paper

10

15

Fig. 7 Low magnication image for sample S-3. The left inset shows

20

an HRTEM image at the lmsubstrate interface of the same sample.

The right inset shows an electron diraction pattern from the lm
substrate interface of the same sample.

25

30

35

40

Fig. 8 The SIMS depth proles of Zn, O, Cu and Al of sample S-3.

45

50

samples. Furthermore, the Cu1+ along with high V$$

O concentrations in sample S-1 and more dominant Cu2+ states in S-2
and S-3 are found responsible for highly conducting and insulating behaviour of the respective samples. It seems that CuO
nanophases are playing no role; instead Cu multivalent states
and V$$
O are tuning the conducting and insulating behaviours of
these samples.

55
3.3

Magnetic properties

One of the goals of this investigation is to correlate the magnetic

properties of ZnO:Cu lms with their micro-structural
This journal is The Royal Society of Chemistry 2015

RSC Advances

characteristics. Fig. 9 shows DC magnetization loops at xed

temperature (MH) for all three samples measured at 300 K, aer
proper correction for the diamagnetic term arising from the
substrate. These hysteresis curves provide clear evidence for the
ferromagnetic ordering at room temperature. From these MH
loops, we extracted the saturation magnetization (Ms) values of
0.22  106 emu g1, 0.46  106 emu g1 and 0.04  106
emu g1 and coercive eld (Hc) values of 160 Oe, 53 Oe and
400 Oe for S-1, S-2 and S-3, respectively. The Ms values of all
these samples are relatively lower than the reported values of
ZnO:Cu thin lms and nanostructures3739 indicating extrinsic
origin of magnetization in these samples. Generally, two key
theoretical models, the RudermanKittelKasuyaYosida
(RKKY)-type indirect exchange interactions and boundmagnetic polarons (BMPs) are used to explain the ferromagnetic ordering in DMS materials when the carrier concentration
is well below the impurity concentration.40,41 Presences of CuO
secondary phases in all three samples and the highly resistive
nature of samples S-2 and S-3 would not energetically favor
RKKY interactions and BMP model alone cannot promote FM in
these samples. Therefore, we anticipate that the weak ferromagnetic behaviour is not of a single origin, instead V$$
O , mixed
Cu oxidation states and CuO secondary phases contribute
simultaneously in ZnO:Cu thin lm samples reported in the
present study. The existence of CuO planar nanophases may
give rise to the ferromagnetism in ZnO:Cu20 and the magnetic
susceptibility of these CuO nanophases increases rapidly when
their size decreases. When the CuO sizes are small, the residual
spins of the Cu ions at the interface can couple ferromagnetically with planar spins to generate larger values of the
moment.20,42 On the other hand, in oxygen decient samples the
donoracceptor defect pairs (DAPs) such that Cu  V$$
O , can play
a signicant role on the development of ferromangetic ordering
in the ZnO:Cu system.18,37
In MH loops shown in Fig. 9, the S-1 sample shows intermediate values of Ms and Hc compared to the S-2 and S-3
samples. The HRTEM analysis on S-1 showed perfect epitaxial
thin lm growth with a very sharp and clear interface excluding
the possibility of magnetization coming from the interface
distortion or metal clustering at the interface. Moreover, we are
unable to identify other extrinsic sources for the observed weak
ferromagnetism, and these lms are found to be free from
spurious impurities as undoped ZnO lms prepared under
identical conditions failed to detect any ferromagnetism (not
shown here) ruling out the deposition chamber and sample
handling as a potential cause of contamination. Possible sources for the observed magnetization in the S-1 sample are small
size CuO nanophases (34 nm), mixed Cu oxidation states or
$$
high V$$
O concentration. The isolated VO are known to destroy
$$
the FM in ZnO:Cu system, but VO coupled with mixed Cu
oxidation sates can endorse ferromagnetic ordering.18,37 Due to
mixed oxidation states of Cu in sample S-1, the eective
1
Cu2  V$$
defect complexes may give rise to magnetic
O  Cu
ordering. The electrons bound to V$$
O would align in an antiparallel spin conguration with the Cu ions, thus resulting in
a parallel spin conguration of the neighboring Cu ions leading
to
an
indirect
double
exchange
ferromagnetic

RSC Adv., 2015, xx, 110 | 7

10

15

20

25

30

35

40

45

50

55

RSC Advances

10

15

20

25

30

35

40

45

50

55

Fig. 9 Room-temperature DC magnetization loop for all three

samples. The upper left inset shows zero eld cooled and eld cooled
for sample S-1. The lower right inset shows magnetoresistance curves
for S-1 sample.

1
Cu2  V$$
network.18 However, S-1 is conducting
O  Cu
(carrier concentration  3.32  1018) and a large amount of V$$
O
concentrations may convert Cu2+ to Cu1+ thereby reducing
1
eective Cu2  V$$
complexes. Therefore, due to the
O  Cu
highly conducting nature of sample S-1, the indirect double
1
exchange ferromagnetic Cu2  V$$
network becomes
O  Cu
less eective in mediating ferromagnetic ordering. On the other
hand, small size CuO crystals oer higher coercivity and create
noticeable changes in the magnetic properties, since CuOCu
superexchange is strongly dependent on both, bond angels and
bond lengths on size reduction.42,43 Therefore, the intermediate
Ms and high Hc of sample S-1 compared to S-2 is mainly originating from ferromagnetic CuOCu superexchange due to
uncompensated Cu spins at the surface of small size CuO
nanophases. These observations are in agreement with previous
reports on doped ZnO and GaN1,5,44 where TM based nanophases were clearly detected and found responsible for the
observed FM. Moreover, we suggest that if an indirect double
1
exchange ferromagnetic Cu2  V$$
network is playing
O  Cu
any role in tuning the magnetism in sample S-1, it is dominated
by the pronounced ferromagnetic signal coming from the
surface of CuO nanophases embedded in the (001) plane of the
ZnO:Cu thin lm host.
In the case of sample S-2, we notice the highest value of Ms
compared to the S-1 and S-3 samples. Although we observe
relatively lower epitaxial quality of S-2 sample compared to S-1
sample, the HRTEM analysis still showed epitaxial thin lm
growth along with the presence of CuO nanophases. This
reveals that the high Ms value is not coming from the interface
distortion or metal clustering at the interface. Core level XPS
study for sample S-2 showed a more dominant Cu2+ signal than
$$
Cu1+ with small amount of V$$
O concentration. This low V O
2+
1+
$$
concentrations leads to high Cu /Cu ratio and the VO have

8 | RSC Adv., 2015, xx, 110

Paper

better chances to couple with Cu2+ to generate more eective

1
Cu2  V$$
complexes. Furthermore, the S-2 sample
O  Cu
shows the lowest value of Hc compared to the S-1 and S-3
samples, which suggests much less contribution of CuOCu
ferromagnetic superexchange interaction of the CuO nanophases to the observed FM. Therefore, the observed lowest Hc
and highest Ms values for sample S-2 suggest dominant
1
behaviour of ferromagnetic Cu2  V$$
indirect double
O  Cu
exchange interactions over CuOCu ferromagnetic superexchange interaction of CuO nanophases in tuning the RT FM.
Finally, sample S-3 shows a very weak and distorted magnetization signal with the highest value of Hc. As discussed previously, we observe a relatively larger size of CuO (810 nm)
nanophases and poor crystal quality of this high oxygen partial
pressure grown sample. The XPS analysis also indicated a
substantial decrease in V$$
O concentration resulting in a
1
comprehensive reduction of the Cu2  V$$
networks.
O  Cu
Therefore, the increased Hc might be due to more pronounced
eect of large size CuO nanophase inclusion and the lowest Ms
is originating from a reduced number of ferromagnetic indirect
1
double exchange Cu2  V$$
defect complexes.
O  Cu
In the above discussed scenario, the HRTEM analysis unveils
a systematic localized epitaxial disorder, but changes in the MH
loop are not regular with increase in oxygen pressure during the
thin lm growth. We observe intermediate values of Ms and Hc
for the best quality sample S-1 and the highest value of Ms for
the relatively low quality sample S-2. HRTEM and MH loops
studies suggest that the thin lm quality seems to play very little
eective role in governing the FM. On the other hand, the
magnetic properties of ZnO:Cu thin lm samples are highly
tuneable by the presence of CuO nanophases, multivalent Cu
and V$$
O concentrations.
XRD and HRTEM analyses on sample S-1 show the best
epitaxial quality for this sample. To further conrm the existence of magnetic CuO phases in sample S-1, we carried out ZFC
and FC magnetization (M) versus temperature measurements
with 100 Oe applied eld through a temperature range of 1.5 to
350 K. One of the important signatures of nanosized magnetic
particles is the separation of ZFC and FC curves below the
characteristic blocking temperature (TB). Fig. 9 (upper le inset)
shows a clear bifurcation of the ZFC and FC data and the onset
of irreversibility starts at room temperature. The splitting
between the FC and ZFC data curves strongly suggests the
presence of superparamagnetic blocking in the magnetic
nanophase. The ZFC magnetization curve shows a maximum at
TB z 210 K, which is the blocking temperature corresponding
to the smallest crystal size. The bulk CuO crystallizes in a
monoclinic structure and experiments demonstrate an incommensurate antiferromagnetic phase transition between TN1
230 K and TN2 213 K, with a commensurate AFM phase below
TN2 due to a magnetolattice coupling eect.45 Small size CuO
particles are known to acquire ferromagnetic order due to
residual spins of the Cu ions at the cluster interface42 and the
lattice distortion, as evidenced in HRTEM, can promote FM
superexchange interaction in CuOCu complexes.46 Therefore,
the bifurcation in the ZFC and FC curves and the evolution of a
broad peak around TB z 210 K in the ZFC curve suggest

This journal is The Royal Society of Chemistry 2015

10

15

20

25

30

35

40

45

50

55

Paper

10

15

20

25

30

35

40

45

50

55

presence of CuO nanophases that carry the basic magnetic

moment in sample S-1. Furthermore, a large separation
between onset of irreversibility (z300 K) and blocking
temperature (TB z 210 K) in the ZFC curve demonstrate that
CuO nanophases have widely distributed sizes. The blocking
temperature can be related to the volume (V) of the smallest
moment-carrying entity in the system by the relation 25kBTB
KV.43 Here kB is the Boltzmann constant and K is the anisotropy
constant. Using TB 210 K, and K 2  106 erg cm3 for typical
transition metal oxides,47,48 the eective average crystal size is
7 nm for sample S-1. This eective average crystal size (7 nm)
is larger than that obtained by TEM measurements (34 nm) for
the S-1 sample. The larger eective crystal size measured by the
ZFC/FC magnetization may possibly arise from relevant interparticle magnetic interactions due to presence of a high density
of CuO nanocrystals in sample S-1 as evidenced by TEM analysis.49 The large dierence between the crystallite sizes
measured from TEM and ZFC/FC curves also indicates the wide
distributions of CuO crystallite sizes, as evident by broad peak
at TB 210 K in ZFC magnetization curve.
Apart from the magnetization measurements, a further and
important way to check the existence of magnetic order is the
measurement of the magnetotransport properties. Our HRTEM
and ZFC/FC measurements have revealed that sample S-1 is
inhomogeneous and consists of regions of dierent magnetic
properties. Depending on the size, distribution, and density of
the inhomogeneous regions, their eect should be reected in
the transport properties.4 We observed a negative magnetoresistance (Fig. 9 lower right inset) in the S-1 sample. The
magnetoresistance (MR) is dened as [R(H)  R(0)]/R(0), where
R(H) and R(0) are the resistances with and without an applied
magnetic eld, respectively.50 The MR strongly depends on
temperature, changing from large negative MR (15%) at low
temperatures to a small negative MR at high temperatures in
the low eld regions. The strongly negative MR is the indication
of an extrinsic origin of FM and absence of carrier mediated
ferromagnetism. The negative MR has also been observed in
several homogenous and inhomogeneous magnetic ZnO
systems.5153 In case of inhomogeneous magnetic ZnO systems
just like our S-1 sample, the negative MR may be related to spindependent tunnelling between or across CuO regions carrying
ferromagnetic ordering.4,53

4. Conclusions
We have studied PLD grown ZnO:Cu thin lms prepared under
dierent oxygen partial pressures. All the samples contain CuO
secondary phases irrespective of the growth conditions. An
increase in oxygen partial pressure during growth leads to the
reduction in the (002) peak and enhancement in FWHM of this
peak suggesting degradation in the epitaxial quality of the
ZnO:Cu lm. Core level XPS result shows existence of mixed Cu
oxidation states and CuO secondary phases. Detailed HRTEM
analysis reveals that an increase in oxygen growth pressure
degrades the epitaxy of these thin lm samples due to the
inclusion of nanosize CuO in the ZnO host lattice. The magnetic
properties of ZnO:Cu thin lm samples are highly tuneable by
This journal is The Royal Society of Chemistry 2015

RSC Advances

the simultaneous presence of CuO nanophases, multivalent Cu

and V$$
O concentrations. The very broad peak in the ZFC
magnetization and the strongly negative MR signal that originates from ferromagnetic nanosize CuO regions further
conrms the extrinsic FM in the high quality S-1 sample.

Acknowledgements
The work presented here was supported by the Research Grant
Council of HKSAR under the GRF scheme (HKU703612P), as
well as HKUST DAG12SC05-4, FSGRF12SC13 and HKU Seed
Funding Program for Basic Research (201111159037).

10

15

References
1 Bonanni, A. N. Quezada, T. Li, M. Wegscheider, Z. Matej,
V. Holy, R. T. Lechner, G. Bauer, M. Rovezzi, F. D. Acapito,
M. Kiecana, M. Sawicki and T. Diet, Phys. Rev. Lett., 2008,
101, 135502.
2 K. Sato, H. Katayama-Yoshida and P. H. Dederichs, Jpn. J.
Appl. Phys., Part 2, 2005, 44, L948.
3 M. Younas, L. L. Zou, M. Nadeem, Naeem-ur-Rehman,
S. C. Su, Z. L. Wang, W. Anwand, A. Wagner, J. H. Hao,
C. W. Leung, R. Lortz and F. C. C. Ling, Phys. Chem. Chem.
Phys., 2014, 16, 16030.
4 M. Tay, Y. Wua, G. C. Han, T. C. Chong, Y. K. Zheng,
S. J. Wang, Y. C. and X. Pan, J. Appl. Phys., 2006, 100, 063910.
5 T. Dietl, Nat. Mater., 2010, 9, 965.
6 K. R. Kittilstved, W. K. Liu and D. R. Gamelin, Nat. Mater.,
2006, 5, 291.
7 K. R. Kittilstved, N. S. Norberg and D. R. Gamelin, Phys. Rev.
Lett., 2005, 94, 147209.
8 M. Venkatesan, C. B. Fitzgerald, J. G. Lunney and
J. M. D. Coey, Phys. Rev. Lett., 2004, 93, 177206.
9 P. Sharma, A. Gupta, K. V. Rao, F. J. Owens, R. Sharma,
R. Ahuja, J. M. Osorio-Guillen, B. Johansson and
G. A. Gehring, Nat. Mater., 2003, 2, 673.
10 J. M. D. Coey, M. Venkatesan and C. B. Fitzgerald, Nat.
Mater., 2005, 4, 173.
11 M. Venkatesan, C. B. Fitzgerald, J. G. Lunney and
J. M. D. Coey, Phys. Rev. Lett., 2004, 93, 177206.
12 L. M. Huang, A. L. Rosa and R. Ahuja, Phys. Rev. B: Condens.
Matter Mater. Phys., 2006, 74, 075206.
13 Q. Ma, D. B. Buchholz and R. P. H. Chang, Phys. Rev. B:
Condens. Matter Mater. Phys., 2008, 78, 214429.
14 L. H. Ye, A. J. Freeman and B. Delley, Phys. Rev. B: Condens.
Matter Mater. Phys., 2006, 73, 033203.
15 L. M. Huang, A. L. Rosa and R. Ahuja, Phys. Rev. B: Condens.
Matter Mater. Phys., 2006, 74, 075206.
16 M. H. N. Assadi, Y. B. Zhang and S. Li, J. Phys.: Condens.
Matter, 2010, 22, 486003.
17 T. F. Shi, Z. G. Xiao, Z. J. Yin, X. H. Li, Y. Q. Wang, H. T. He,
J. N. Wang, W. S. Yan and S. Q. Wei, Appl. Phys. Lett., 2010,
96, 211905.
18 T. S. Herng, D. C. Qi, T. Berlijn, J. B. Yi, K. S. Yang, Y. Dai,
Y. P. Feng, I. Santoso, C. S. Hanke, X. Y. Gao, A. T. S. Wee,

RSC Adv., 2015, xx, 110 | 9

20

25
6
7

30

35

40

45

50

55

RSC Advances

1
19
5

20
21

10

22
23

15

24
25
26

20

27
28

25

29
30

30

31
32

35

33
34
35

40

36

W. Ku, J. Ding and A. Rusydi, Phys. Rev. Lett., 2010, 105,

207201.
K. R. Kittilstved, D. A. Schwartz, A. C. Tuan, S. M. Heald,
S. A. Chambers and D. R. Gamelin, Phys. Rev. Lett., 2006,
97, 037203.
C. Sudakar, J. S. Thakur, G. Lawes, R. Naik and V. M. Naik,
Phys. Rev. B: Condens. Matter Mater. Phys., 2007, 75, 054423.
D. Huang, Y. J. Zhao, D. H. Chen and Y. Z. Shao, Appl. Phys.
Lett., 2008, 92, 182509.
Q. Ma, D. B. Buchholz and R. P. H. Chang, Phys. Rev. B:
Condens. Matter Mater. Phys., 2008, 78, 214429.
L. H. Ye, A. J. Freeman and B. Delley, Phys. Rev. B: Condens.
Matter Mater. Phys., 2006, 73, 033203.
H. Liu, F. Zeng, S. Gao, G. Wang, C. Song and F. Pan, Phys.
Chem. Chem. Phys., 2013, 15, 13153.
Y. Tian, Y. Li, M. He, I. A. Putra, H. Peng, B. Yao, S. A. Cheong
and T. Wu, Appl. Phys. Lett., 2011, 98, 162503.
J. Sohn, S. H. Song, D. W. Nam, I. T. Cho, E. S. Cho, J. H. Lee
and H. I. Kwon, Semicond. Sci. Technol., 2013, 28, 015005.
S. Poulston, P. M. Parlett, P. Stone and M. Bowker, Surf.
Interface Anal., 1996, 24, 811.
J. F. Moulder, W. F. Stickle, P. E. Sobol and K. D. Bomben,
Handbook of X-ray Photoelectron Spectroscopy, Perkin-Elmer,
Eden Prairie, 1992.
D. Chakraborti, J. Narayan and J. T. Prater, Appl. Phys. Lett.,
2007, 90, 062504.
M. C. Biesinger, L. W. M. Laua, A. R. Gerson and
R. S. C. Smart, Appl. Surf. Sci., 2010, 257, 887.
M. S. Park and B. I. Min, Phys. Rev. B: Condens. Matter Mater.
Phys., 2003, 68, 224436.
T. S. Herng, S. P. Lau, S. F. Yu, H. Y. Yang, X. H. Ji, J. S. Chen,
N. Yasui and H. Inaba, J. Appl. Phys., 2006, 99, 086101.
M. Scrocco, Chem. Phys. Lett., 1979, 63, 52.
L. M. Kukreja, P. Misra, J. Fallert, D. M. Phase and H. Kal, J.
Appl. Phys., 2012, 112, 013525.
D. O. Klenov, G. N. Kryukova and L. M. Plyasova, J. Mater.
Chem., 1998, 8, 1665.
B. Fultz and J. M. Howe, Transmission Electron Mircoscopy
and Diractometry of Materials, Springer, Berlin, 2nd edn,
2002.

Paper

37 L. Hu, J. Huang, H. He, L. Zhu, S. Liu, Y. Jin, L. Sun and Z. Ye,

Nanoscale, 2013, 5, 3918.
38 G. Z. Xing, J. B. Yi, J. G. Tao, T. Liu, L. M. Wong, Z. Zhang,
G. P. Li, S. J. Wang, J. Ding, T. C. Sum, C. H. A. Huan and
T. Wu, Adv. Mater., 2008, 20, 3521.
39 L. Hu, L. Zhu, H. He and Z. Ye, Appl. Phys. Lett., 2014, 105,
072414.
40 Dietl, H. Ohno and F. Matsukura, Phys. Rev. B: Condens.
Matter Mater. Phys., 2001, 63, 195205.
41 M. J. Calderon and S. D. Sarma, Ann. Phys., 2007, 322, 2618.
42 A. Punnoose, H. Magnone, M. S. Seehra and J. Bonevich,
Phys. Rev. B: Condens. Matter Mater. Phys., 2001, 64, 174420.
43 B. D. Cullity and C. D. Graham, Introduction to Magnetic
Materials, Wiley, Hoboken, 2nd edn, 2009.
44 L. C. Nistor, C. Ghica, V. Kuncser, D. Pantelica, J. J. Grob,
G. Epurescu and M. Dinescu, J. Phys. D: Appl. Phys., 2013,
46, 065003.
45 H. Yamada, X. G. Zheng, Y. Soejima and M. Kawaminami,
Phys. Rev. B: Condens. Matter Mater. Phys., 2004, 69, 104104.
46 D. B. Buchholz, R. P. H. Chang, J. H. Song and J. B. Ketterson,
Appl. Phys. Lett., 2005, 87, 082504.
47 A. Dinia, G. Schmerber, V. P. Bohnes, C. Meny, P. Panissod
and E. J. Beaurepaire, J. Magn. Magn. Mater., 2005, 286, 37.
48 B. Ghosh, M. Sardar and S. Banerjee, J. Phys. D: Appl. Phys.,
2013, 46, 135001.
49 R. Torchio, C. Meneghini, S. Mobilio, G. Capellini,
A. G. Prieto, J. Alonso, M. L. F. Gubieda, V. T. Liveri,
A. Longo, A. M. Ruggirello and T. Neisius, J. Phys.: Conf.
Ser., 2010, 200, 72100.
50 M. Khalid and P. Esquinazi, Phys. Rev. B: Condens. Matter
Mater. Phys., 2012, 85, 134424.
51 P. A. Lee and V. Vramakrishnan, Rev. Mod. Phys., 1985, 57,
287.
52 H. Ohno, H. Munekata, T. Penney, S. Von Molnar and
L. L. Chang, Phys. Rev. Lett., 1992, 68, 2664.
53 M. Paranjape, J. Mitra, A. K. Raychaudhuri, N. K. Todd,
N. D. Mathur and M. G. Blamire, Phys. Rev. B: Condens.
Matter Mater. Phys., 2003, 68, 144409.

10

15

20

25

30

35

40

45

45

50

50

55

55

10 | RSC Adv., 2015, xx, 110

This journal is The Royal Society of Chemistry 2015