Journal of Alloys and Compounds 588 (2014) 705709

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Journal of Alloys and Compounds

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

Structural, optical and magnetic characterization of Ru doped ZnO

nanorods
Sanjeev Kumar a,f,, Palvinder Kaur b, C.L. Chen c,e, R. Thangavel d, C.L. Dong e, Y.K. Ho c,e, J.F. Lee e,
T.S. Chan e, T.K. Chen c, B.H. Mok c, S.M. Rao b,c, M.K. Wu c
a

University College of Engineering, Punjabi University, Patiala 147002, India

Department of Physics, Punjabi University, Patiala 147002, India
Institute of Physics, Academia Sinica, Taipei 11529, Taiwan
d
Department of Applied Physics, Indian School of Mines, Dhanbad 826004, India
e
National Synchrotron Radiation Research Center (NSRRC), Hsinchu 30076, Taiwan
f
Department of Applied Sciences, PEC University of Technology, Chandigarh 160012, India
b
c

a r t i c l e

i n f o

Article history:
Received 16 September 2013
Received in revised form 15 November 2013
Accepted 21 November 2013
Available online 27 November 2013
Keywords:
Oxides
Nanostructures
Solgel chemistry
XAFS
X-ray diffraction
Crystal structure

a b s t r a c t
Ruthenium (Ru = 0%, 1% and 2%) doped nano-crystalline zinc oxide (ZnO) nanorods were synthesized by
using well-known solgel technique. X-ray diffraction (XRD) results show that Ru (0%, 1% and 2%) doped
ZnO nanorods crystallized in the wurtzite structure having space group C3v (P63mc). Williamson and Hall
plot reveal that in the nanoscale dimensions, incorporation of Ru induced the tensile strain in ZnO host
matrix. Photoluminescence (PL) and Raman studies of Ru doped ZnO nanorods show the formation of singly ionized oxygen vacancies which may account for the observed room temperature ferromagnetism
(RTFM) in 2% Ru doped ZnO. X-ray absorption spectroscopy (XAS) reveals that Ru replace the Zn atoms
in the host lattice and maintain the crystal symmetry with slightly lattice distortion.
2013 Elsevier B.V. All rights reserved.

1. Introduction
During last two decades, wide band gap diluted magnetic semiconductors exhibiting Curie temperature above 300 K have received great attention [13]. Investigations on transition metal
(TM) doped ZnO have intensied after theoretical prediction of
the possibility of room temperature ferromagnetism (RTFM) in
Mn doped ZnO [4]. RTFM have been reported in ZnO doped with
3d transition metal such as Ni, Cu, Cr, Mn, and Co [59], which
makes ZnO, a promising material for spintronics based applications. These transition metal dopant ions are ferro-magnetically
coupled leading to spin polarization of the charge carriers of the
semiconductor. Though, in transition metals (TMs), the 3d electrons are exterior and delocalized leading to strong direct exchange
interactions. Consequently, total magnetic moment per atom is
small because of nil orbital momentum. Co doped ZnO is the major
studied system possessing RTFM [1014].
Different research groups, also reported the doping of 4d TMs in
ZnO, like Ag doping for optical and electrical properties [15], Pd
Corresponding author. at: University College of Engineering, Punjabi University,
Patiala 147002, India. Tel.: +91 8968354516.
E-mail address: sanjeev04101977@gmail.com (S. Kumar).
0925-8388/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.11.137

doping for humidity sensing [16], Nb doping for transparent conducting oxide [17], Cd doping for electrical properties [18], and observed lower resistivity by doping with Zr [19]. Yun et al.
calculated theoretically the electronic structure and magnetism
of 3d and 4d TM-doped ZnO (TM = Ti, Cr, Mn, Fe, Co, Ni, Ru, Pd,
and Ag), using the highly precise full-potential linearized augmented plane wave (FLAPW) method [20].
Navale et al. [21] reported the high sensitivity of Ru doped ZnO
nanoparticles synthesized by simple citrate gel route. Hsi et al. [22]
reported the increase in electrical conductivity of Al doped ZnO
thin lms with additional doping of Ru. They suggested that the
Ru ions substitute the Zn ions and provides extra two free electrons, this might considerably inuence the microstructure and
hence electrical behavior of Al-doped ZnO thin lm. Kim et. al.
[23] reported the Ru doping in SnO2 hollow spheres and showed
that the consequent change in donor density increase the gas sensing response. Wang et al. [24] presented the practical application
of Ru doped spinel-structured transition metal oxides as cathode
materials for the next generation of high power lithium-ion
batteries.
Here we report the structural, optical and magnetic properties
of Ru (0%, 1% and 2%) doped ZnO nanorods synthesized using
solgel technique. As per literature survey, no report is available

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S. Kumar et al. / Journal of Alloys and Compounds 588 (2014) 705709

on the magnetism in Ru doped ZnO nanorods synthesized using sol

gel technique.
2. Experimental
Ru doped ZnO nanorods were synthesized by solgel technique. Zinc acetate
dihydrate, ruthenium chloride, 2-methoxyethanol and monoethanolamine (All
chemicals were purchased from Sigma Aldrich) were used as the starting materials,
solvent and stabilizer, respectively. Zinc acetate dihydrate and ruthenium chloride
were rst dissolved in 2-methoxyethanol. The molar ratios of monoethanolamine to
zinc acetate dihydrate were maintained at 1. Then, the resulting mixture was stirred at 60 C for 2 h. When the mixture was stirred, monoethanolamine was added
drop by drop. Finally, a clear and transparent homogeneous solution was formed.
The total concentration of solution was kept at 0.5 mol/L and the concentration of
Ru dopant was 1 and 2 mol% with respect to zinc. The sol was aged for 24 h at room
temperature. Then we dried the sol in a furnace at 500 C for 1 h and crushed the
dry samples in pestle mortar to get the ne powder. Then we again annealed the
ne powder at 500 C for 1 h to completely remove organic impurities.
The structural properties of Ru doped ZnO nanorods were investigated using
Panalytical Xpert Diffractometer. The nanorod size determination and structure
conrmations were made using a JEOL High Resolution Transition Electron Microscope (HR-TEM). Photoluminescence (PL) and Raman spectroscopy measurements
were carried out using a Horiba Jobin Yvon HR-800 UV micro-PL Raman setup.
The 325 nm line of a HeCd laser was used as the excitation source with a
2400 grooves/mm grating in the backscattering geometry. Magnetic measurements
were made using a Quantum Design Vibrating Sample Magnetometer (VSM). The Xray absorption near-edge structure (XANES) measurements were performed at the
National Synchrotron Radiation Research Center (NSRRC) in Taiwan operated at
1.5 GeV with a maximum stored current of 200 mA. The hard X-ray measurements
were recorded with a spacing of 0.3 eV for the XANES in the uorescence yield (FY)
mode using a Lytle detector at room temperature, using a Si (1 1 1) double crystal
mono-chromator in BL01C and BL17C beamline. All spectra were normalized to a
unity step height in the absorption coefcient from well below to well above the
edge. Standard oxide samples of ZnO, RuO2 and the foils of Zn and Ru were used
for energy calibration and also for comparing the different electronic valence states.

3. Results and discussion

Fig. 1 presents the XRD patterns and their Rietveld renements
achieved using FullProf software. PseudoVoigt function was
y obs
y calc

undoped ZnO

y obs-y calc

adopted to carry out Rietveld renement of all the samples with

the space group P63mc. During the Rietveld renement, wurtzite
structure of ZnO was preferred as starting model structure and
Ru ions were supposed to be substituted into the ZnO lattice occupying Zn2+ sites. No peaks related to the impurities were observed,
depicting the entire incorporation of Ru into the ZnO host matrix.
With increase in Ru concentration, peaks get shifted towards lower
angles, depicting the increase in lattice constant. The average crystallite size is calculated from the full width at half maximum
(FWHM) of the intense diffraction peak (1 0 1) (calculated using
the Scherrer formula; D = kk/b cos h where h is the diffraction angle,
b is the FWHM of the diffraction peak, k is the geometric factor
(0.9) and D is the mean crystallite size) is found to be
24 1 nm, 27 1 nm and 29 1 nm for undoped, 1% Ru and 2%
Ru doped ZnO nanopowder, respectively. Navale et al. [21] also observed the crystallite size of Ru doped ZnO powders in the similar
range. The relative displacement between Zn and O sub-lattices
along the c-axis which is measured through local wurtzite parameter (u = a2/3c2 + 0.25), is found to decrease and the c/a ratio to increase with increase in Ru doping. This small distortion in
structure originated due to the bond-length variation may be reason for the RTFM observed in 2% Ru doped ZnO.
The FWHM of any diffraction peak can be expressed as linear
combination of the contribution from lattice strain and small grain
size (using Hall and Williamson relation (b cos h/k = 1/D + g sin h/k,
where g is the effective strain). Fig. 2 represents the plot between
b cos h/k and sin h/k for (1 0 1) peak of Ru doped ZnO nanorods. The
graph has a positive slope indicating a tensile strain. From the
XRD patterns, it is observed that peak positions shift towards lower
2h value with increasing Ru doping indicating slight increase in the
lattice parameters. The ionic radius of Zn2+ (74 pm) being lower
than Ru4+ (130 pm) [21], the inclusion of Ru in the ZnO modies
the lattice parameters (minor increase in the a parameter and major increase in c parameter) in corroboration with the lattice strain
as well as shifting of peaks towards lower angle in XRD pattern. It is
already reported that for Ru doped ZnO, there is marginal increase
in the a parameter and signicant increase in c parameter in comparison with undoped ZnO [21]. Fig. 3 shows typical HR-TEM image
of Ru doped ZnO nanorods depicting the average diameter of Ru
doped ZnO nanorods around 200 nm. Fig. 3 also presents the selected area electron diffraction (SAED) pattern conrming the single phase of solgel synthesized Ru doped ZnO nanorods. The
intense points observed in the SAED pattern indicates Ru doped
ZnO nanorods consists of bigger crystallites, as corroborates with
the crystallite size (2730 nm) calculated using Scherrer formula.

Intensity (a.u.)

y obs
y calc

1% Ru doped ZnO

2.0

y obs-y calc

Cos/ (10 )

1.9

y obs
y calc

2% Ru doped ZnO

y obs-y calc

1.9

1.8

1.8
30

35

40

45

50

55

60

65

70

Angle (2)
Fig. 1. XRD patterns of Ru doped ZnO nanorods synthesized using the solgel
technique.

3.8325

3.8400

3.8475

3.8550

Sin/ (10 )
Fig. 2. Willamson and Hall plot of Ru doped ZnO nanorods synthesized using the
solgel technique.

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S. Kumar et al. / Journal of Alloys and Compounds 588 (2014) 705709

Fig. 3. TEM micrograph of Ru doped ZnO nanorods synthesized using the solgel technique and the SAED pattern of Ru doped ZnO nanorods.

The room temperature photoluminescence (PL) spectra of Ru

(0%, 1% and 2%) doped ZnO nanorods (Fig. 4ac), was obtained utilizing a HeCd laser of 328 nm wavelength as the excitation source.
The PL spectra were de-convoluted in three different peaks tabulated in Table 1 for 1% and 2% Ru doped ZnO, while in case of undoped ZnO there is only one peak corresponding to near band edge
emission is observed indicating absence of defects. Strong peak observed around 397 nm in 1% Ru doped ZnO, reveals a red shift as
compared with the reported near band-edge emission for pure
ZnO (385 nm) [25]. Incorporation of dopant ions introduces a shallow energy level near valence band. Thus, the observed red shift
could be attributed to the defects and the likely shallow energy
levels [2527]. The violet emission observed around 419 nm is
associated to oxygen vacancies [28,29].
The strong violet emission observed around 412 nm in 2% Ru
doped ZnO is again red shifted to higher value may be associated
to oxygen vacancies [28,29]. Usually, the near band emission in
ZnO is reported between 385 and 395 nm; the lower value of

Normalized PL Intensity

2% Ru doped ZnO

1% Ru doped ZnO

undoped ZnO

400

500

600

700

Wavelength (nm)
Fig. 4. Room temperature PL spectra of Ru doped ZnO nanorods synthesized using
the solgel technique.

Table 1
Photoluminescence peak positions in the Ru doped ZnO nanorods.
Ru concentration (%)

0
1
2

PL peak positions
Peak I (nm)

Peak II (nm)

Peak III (nm)

386
397
412

419
449

542
550

bandgap in the Ru doped ZnO nanorods may be attributed to the

oxygen-decient non-stoichiometric nature of the materials [25].
The violet blue emission peak around 449 nm may be credited to
the exciton recombination between the holes in the valence band
and electron localized at the interstitial zinc [3032]. Weak green
emission peak observed around 542 nm and 550 nm for 1% and
2% Ru doped ZnO, respectively may be due to the transition between singly ionized oxygen vacancy and photoexcited hole, [33]
or transition between a deeply trapped hole at Vo++ [34] surface defects [35] and electron close to the conduction band. Green emission is usually related with oxygen deciency while yellow/
orange emission is related with excess oxygen [36]. The decrease
in the bandgap of ZnO with increase in Ru doping increases the
suitability of these materials for nano-optoelectronic devices.
Raman active modes of 322 cm 1 for E2 high-E2 low, 448 cm 1
for E2 (high), 573 cm 1 for 1st order A1 (LO), 747 cm 1 for A1
(LA + TO), 1150 cm 1 for 2nd order A1 (LO), 1731 cm 1 3rd order
A1 (LO) and 2296 cm 1 4th order A1 (LO) have been reported for
solgel synthesized ZnO [37]. The strong peak at about 448 cm 1
is reported to the high frequency branch of the E2 mode i.e. E2
(high) of ZnO, which is a Raman active mode in the wurtzite crystal
structure. From Fig. 5 clear blue shift is observed for the peak corresponding to E2 (high) mode for Ru doped ZnO nanorods. Stress
induced in the wurtzite-structure affects the E2 phonon frequency
[38]. An increase in the E2 phonon frequency is ascribed to compressive stress, whereas a decrease in the E2 phonon frequency is
ascribed to a tensile stress. We also observed decrease in E2 phonon frequency attributes to tensile strain, corroborates with Williamson and Hall plot. It is generally agreed that this stress arises
from a mismatch in the thermal expansion coefcients of the
nanorods.
Fig. 6a shows the Zn K-edge XANES spectra of different Ru
doped ZnO samples along with undoped ZnO standard. The main
peaks between 9665 and 9674 eV is associated with the transition
from Zn 1s to empty 4p non-bonding states. No chemical shift is
observed, implying the Zn is divalent. The spectral shapes are
basically unaffected by doping. This result is also observed in the
Zn L3-edge as shown in the inset of the gure. However, the

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S. Kumar et al. / Journal of Alloys and Compounds 588 (2014) 705709

Absorption Intensity (a.u.)

Raman Intensity (a.u.)

undoped ZnO
1% Ru ZnO
2% Ru ZnO

ZnO-2% Ru
D
C

ZnO-1% Ru

RuO2 standard
500

1000

1500

2000

2500

3000

-1

Wavenumber (cm )

2832

Fig. 5. Raman spectra of Ru doped ZnO nanorods synthesized using the solgel
technique.

intensity of the main peak, as indicated by the vertical dot line, becomes weak as Ru content increases. This indicates the Ru would
substitute the Zn site and maintain the crystal symmetry with
slightly lattice distortion.
Fig. 6b shows the XANES O K-edge spectra of Ru doped ZnO for
various values of Ru content, along with undoped ZnO standard. All

Zn K-edge

Absorption intensity (a.u.)

ZnO-2%Ru
ZnO-1%Ru

Zn L-edge

ZnO-2%Ru
ZnO-1%Ru
ZnO

ZnO

1000

9660

1010

9670

1020

1030

9680

Photon Energy (eV)

Fig. 6a. Zn K edge absorption spectra of Ru doped ZnO nanorods.

Absorption intensity (a.u.)

O K-edge

ZnO-1%Ru

ZnO-1%Ru

ZnO

520

524

528
532
Photon Energy (eV)

536

540

Fig. 6b. O K edge absorption spectra of Ru doped ZnO nanorods.

2836

2840

2844

2848

Photon Energy (eV)

Fig. 6c. Ru L3-edge spectra Ru doped ZnO nanorods along with RuO2 standard.

the spectra are normalized to the highest peak at 532 eV. The
spectral shapes revealed the wurtzite structure. Moreover, these
spectra provide the partial density of the O 2p states at the oxygen
site, which are hybridized with TM d and sp bands, and are sensitive to the local structure and the type of the nearest neighbors
[39]. The relatively narrow pre-peak feature B in the photon energy
range 524.2 eV is due to the transition of electrons from O 1s to the
unoccupied O 2p states that are hybridized with Ru 4d states. The
3d orbitals of Zn2+ are fully occupied. Any change of the spectra is
due to the unoccupied Ru 4d orbital [39]. Indeed, the enhancement
of peak B is attributed to the increase in holes through the O 2p Ru 4d hybridization.
Fig. 6c shows the Ru L3-edge spectra along with RuO2 standard.
The features shows two strong lines marked C at lower and D at
higher energy. As Ru occupied at Zn site, the Ru L3-edge XANES
spectra exhibit two peaks which are ascribed to the electric dipole
allowed transitions from the Ru 2p level to the 4d ones (eg and t2g
corresponds to peak C and peak D, respectively) split by the crystal
eld in tetrahedral symmetry in the wurtzite structure of ZnO [39].
Hence this is due to crystal eld effect, where the 10Dq is around
2.6 eV in the Ru content samples. This value is larger than that of
RuO2. The crystal eld splitting is different from the rutile structure
RuO2 standard (octahedral symmetry) [40]. The eg band is more
sensitive to the changes in the bond angle/length as evidenced
by our absorption spectra. The bandwidth is affected largely by
the environment of the Ru ions. The Ru4+ ions replace the Zn site
leads to distorted wurtzite ZnO. The spectra did not observe a large
change in 1% and 2% Ru doping. The result proves that RuO2 may
not exist in the system.
Origin of magnetism in TM-doped ZnO is reported through various models like Zener model, RudermanKittelKasuyaYosida
(RKKY) interaction, indirect double-exchange or super-exchange,
described thoroughly by Djerdj et al. [10]. The magnetization (M)
vs magnetic eld (H) curves for undoped and Ru doped ZnO nanorods are presented in Fig. 7. The hysteresis loops with detectable
coercivity values of 28 Oe and remnant magnetization of
1.74  10 5 emu/g have been obtained for 2% Ru doped ZnO nanorods, while undoped and 1% Ru doped ZnO nanorods shows diamagnetic behavior. Usually ZnO shows diamagnetic behavior. The
valence of Ru being higher than Zn, it works as a donor thereby
varying the distribution of surface defect states [21] and hence is
predictable to induce the magnetism. So with increase in Ru concentration more defects induced corroborates with PL spectra leading to magnetic behaviour. The surface defects induced due to 1%
Ru doping in ZnO may not be so prevalent to induce magnetism.

S. Kumar et al. / Journal of Alloys and Compounds 588 (2014) 705709

References

Magnetic Moment (emu/g)

0.002
undoped ZnO
1% Ru ZnO
2% Ru ZnO

[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
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[10]
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[12]

0.001

0.000

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[13]
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Magnetic Field (Oe)

Fig. 7. MH curves for Ru doped ZnO nanorods at room temperature.

[15]
[16]
[17]
[18]
[19]
[20]

The formation of singly ionized oxygen vacancies is clearly evident

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In solgel synthesized Ru doped ZnO nanorods; surface defects are
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[21]
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4. Conclusions
[31]

In the present study, 1% and 2% Ru doped ZnO nanorods have

been synthesized successfully through solgel method. Structural
analysis indicates that the Ru doped ZnO nanorods crystallized in
the wurtzite structure having space group C3v (P63mc). The XRD
studies using Hall equation reveal that in the nanoscale dimensions, incorporation of Ru induced the tensile strain. Photoluminescence and Raman studies of Ru doped ZnO powder shows the
formation of singly ionized oxygen vacancies which may account
for the observed RTFM in 2% Ru doped ZnO. X-ray absorption spectroscopy (XAS) reveals that Ru replace the Zn atoms in the host lattice and maintain the crystal symmetry with slightly lattice
distortion. The present studies demonstrate that doping of Ru in
ZnO nanostructures gives rise to room-temperature ferromagnetic
ordering which may be useful for spintronic applications.

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