Ceramics International 43 (2017) 8488–8496

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Analysis of structural, optical and magnetic properties of Fe/Co co-doped MARK

ZnO nanocrystals
⁎
Darshan Sharma , Ranjana Jha
Research Lab for Energy Systems, Department of Physics, Netaji Subhas Institute of Technology, University of Delhi, Sector-3, Dwarka, New Delhi 110078,
India

A R T I C L E I N F O A BS T RAC T

Keywords: In this paper, the structural, optical and magnetic properties of pure ZnO and Fe/Co co-doped ZnO
Dilute magnetic semiconductor nanoparticles are presented. Rietveld refinement of XRD pattern revealed the single phase wurtzite structure
C. Optical properties for prepared samples. FTIR study confirmed the formation of tetrahedral coordination between zinc and oxygen
C. Magnetic properties ions. SEM and TEM techniques were used to examine the morphology of samples. The absorption spectra
D. ZnO
showed the decrease in optical energy band gap with Fe/Co co-doping in ZnO. PL spectra demonstrated five
peaks correspond to the ultraviolet region, violet, violet-blue, blue-green and green in the visible region.
Emission peak in the UV region is attributed to near band-edge excitonic emission. Other four emission peaks in
PL spectra are related to different defect states. M-H curve showed room temperature ferromagnetic (RTFM)
behaviour of doped ZnO sample. This paper enhances the understanding of structural, optical and magnetic
properties of Fe/Co co-doped ZnO nanocrystals for application in spintronics, solar cells, and ceramics.

1. Introduction Doping of two TM ions in ZnO is considered as a promising

In spintronics, diluted magnetic semiconductors (DMSs) have at-
tracted the great interest of numerous research groups [1–3]. Both spin
and charge are utilized in spintronic device which includes LEDs, FETs,
spin-based quantum computers, memory devices and solar cells. Room
temperature ferromagnetism is most sought behaviour in DMSs for
practical realization of spintronic devices. RTFM could be achieved
through transitional metal (TM) ions doping in semiconductors [4–8].
Optical properties can also be tuned by doping of TM ions in semicon-
ductors [4,5]. In addition, physical properties of nanocrystals can be
modified with its size and surface functionality. Numerous research groups
have studied the TM doped semiconductors with RTFM nature [9–15].
Zinc Oxide (ZnO) is an optically transparent II-VI semiconductor
which has direct band gap (Eg~3.37 eV at 300 K), large exciton binding
energy (~60 meV) and wurtzite crystal structure. ZnO is considered as
a most popular host material for TM ions doping. Theoretical studies
have predicted ferromagnetism above room temperature for TM
element doped ZnO based DMS devices [2,16]. Different research
groups investigated the effect of various TM doping in ZnO. The
observed magnetic properties have been explained with the help of
different mechanisms such as defects, secondary phase, TM clusters,
impurity phase, bound magnetic polarons (BMPs) and vacancies
[4,13,17–24].
alternative technique to achieve RTFM [25]. Some studies reported
Fe-Ni [26], Co-Mn [27,28], Co-Cu [29], Co-Cr [30], Ni-Mn [13,31], Fe-
Cu [32,33], Co-Ga [34], Co-In [35], Co-Fe [36–39] and Fe-Ag [40] ions
co-doped ZnO nanocrystals. Among these dopant ions, origin of RTFM
and optical properties is still a controversial issue for Fe/Co co-doped
ZnO. In a theoretical study of Fe/Co co-doped ZnO nanowire, Ghosh
et al. [36] argued that ferromagnetic or antiferromagnetic state can
exist on the basis of spin alignment locations of TM ions. The magnetic
behaviour explained through the mechanism of Ruderman-Kittel-
Kasuya-Yosida (RKKY) [41–45] or direct exchange interactions. Park
et al. [46] have not found any indication of charge transfer between Fe
and Co ions, hence double exchange mechanism could not explain the
FM behaviour in Fe/Co co-doped ZnO system. In another study,
Karmakar et al. [47] examined the magnetic behaviour of Fe/Co ions
doped ZnO system and found the mixing of ferrimagnetic & ferro-
magnetic behaviours within the nanocrystals. The possible oxidation
state of Fe ions is found to be 3+ rather than 2+ which suggests
possible oxidation of Fe3+ state at the surface of nanocrystals. Dinesha
et al. [48] analysed the magnetic behaviour of Fe/Co co-doped
nanoparticle and proposed the cause of observed RTFM due to RKKY
exchange, BMPs, and disorder defects. Beltrán et al. [37] examined the
magnetic behaviour of Fe doped, Co doped and Fe/Co co-doped ZnO
nanoparticles. Presence of RTFM in these nanoparticles was attributed

⁎
Corresponding author.
E-mail addresses: dsharma0901@gmail.com (D. Sharma), drranjanajha@gmail.com (R. Jha).

http://dx.doi.org/10.1016/j.ceramint.2017.03.201
Received 16 October 2016; Received in revised form 25 February 2017; Accepted 31 March 2017
Available online 02 April 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
D. Sharma, R. Jha
to the role of charge transfer involving mixed valence ions (Co2+ and
Fe3+).
In another interesting study, Beltrán et al. [38] proposed the RTFM
nature of Fe/Co co-doped ZnO nanoparticles, possibly because of
charge transfer mechanism related to mixed valence ions (especially
Co3+-Co2+) and the presence of extended defects in the sample. Liu
et al. [49] investigated the magnetic properties of Fe/Co co-doped ZnO
nanowire. The observed RTFM is found due to the carrier-mediated
mechanism, especially RKKY exchange interaction, oxygen vacancies
and interstitial Zn defects. Koseoglu [50] studied the RTFM behaviour
of Fe, Co co-doped ZnO nanoparticles. The improved magnetization in
RTFM is attributed to RKKY interactions, BMPs, and disordered
defects. Yu et al. [51] synthesized the Fe doped and Fe/Co co-doped
ZnO nanoparticles. Existence of secondary spinal phases related to
ZnFe2O4 and CoFe2O4 played a crucial role in observed RTFM nature
of nanoparticles.
Optical properties in Fe/Co co-doped ZnO nanocrystals also found
contradictory in scantily reported literature. Beltrán et al. [38] found a
decrease in optical band gap for increased concentrations of Fe/Co ions
in ZnO. On contrary, Singh et al. [52] observed an increase in optical
energy band gap for Fe/Co co-doped ZnO than pure ZnO nanoparticles.
Less explored optical properties of Fe/Co co-doped ZnO nanocrystals
limit its potential application in optoelectronic devices.
An attempt has been made to resolve the contradictory issues on
magnetic and optical properties through this experimental investiga-
tion. In this study, pure ZnO and Fe/Co co-doped ZnO nanocrystals
were synthesized by co-precipitation technique. Structural, morpholo-
gical, optical and magnetic properties of prepared nanocrystals were
studied to understand the origin of RTFM ordering and optical
properties. It paves the path for further promising application in
spintronic, optoelectronic devices and ceramics.
2. Experimental section
2.1. Materials used
Zinc Nitrate hexahydrate Zn(NO3)2·6H2O (LOBA, AR 98% purity),
Iron(III) Nitrate nonahydrate Fe(NO3)3·9H2O (LOBA, AR 99% purity),
Cobalt (II) Nitrate hexahydrate Co(NO3)2·6H2O (LOBA, AR 99%
purity), Lithium hydroxide monohydrate LiOH·H2O (LOBA, AR
99.5% purity), Ethanol (Merck), Acetone (LOBA, AR 99.5% purity)
and Deionised (DI) water. In synthesis process, all the chemicals were
used of analytical reagent grade without any further treatment.
2.2. Synthesis process
Pure ZnO and doped ZnO samples were synthesized by the co-
precipitation method. In typical synthesis process, an appropriate
proportion of metal nitrate powders were mixed thoroughly and
dissolved in ethanol to obtain homogeneous precursor solution (Sol
A). Another homogeneous aqueous solution (Sol B) of LiOH·H2O was
prepared by dissolving in DI water under continuous stirring at room
temperature. The Sol B was added drop-wise into Sol A under vigorous
stirring to maintain pH ~7. The drop rate of Sol B was set at 20–25
drops per min. The pH of the solution was monitored using digital pH
meter throughout the reaction. The obtained solution was allowed to
relax for next two hours. Then, the precipitate was filtered and washed
with DI water, absolute ethanol and acetone. Afterwards, the precipi-
tate was dried at 120 °C for 12 h in hot air oven. Obtained product was
ground and further sintered at temperature 200 °C for 3 h followed by
grinding to get Zn0.98Fe0.01Co0.01O nanocrystalline powder (sample B).
The whole synthesis process was repeated without adding iron
and cobalt precursors for the synthesis of pure ZnO nanoparticles
(sample A).
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Ceramics International 43 (2017) 8488–8496
2.3. Characterization techniques
XRD patterns for sample A and B were recorded using rotating
angle X-ray diffractometer (Miniflex-II, Riguku, Japan) with Cu Kα
radiation source (λ=1.5406 Å). The morphology of samples was
analysed using scanning electron microscope (JEOL Japan JSM 6610
LV). TEM measurements were done with Technai G2 S-Twin FEI. To
record FTIR spectra of samples, pellets were prepared using KBr. FTIR
spectrometer (Spectrum one, Perkin Elmer instrument, USA) was used
for FTIR measurements in the range of 4000–400 cm−1. Optical
properties of samples were observed using UV–Vis spectrometer
(Perkin Elmer instrument, lamda 25, USA) and PL spectrometer (LS-
45, Perkin Elmer, USA). M-H curves were recorded using vibrating
sample magnetometer (Microsense ADE-EV9).
3. Result and discussions
3.1. X-ray diffraction
The structural information of pure ZnO and doped ZnO nanopar-
ticles were analysed by XRD patterns using Rietveld refinement
method (Fig. 1). In the refinement models, hexagonal wurtzite struc-
ture (C46v, space group P63mc) was considered with standard Wyckoff
positions of Zn, Fe or Co atom (1/3, 2/3, 0) and O atom (1/3, 2/3, z).
The peaks in XRD pattern were indexed using JCPDS file 36–1451. No
extra peaks correspond to Fe, Co, Fe/Co cluster, any other impurity or
secondary phase were observed within the sensitivity limit of XRD. It
confirms single phase, hexagonal wurtzite structure of pure and doped
ZnO sample.
The lattice parameter (a and c) of prepared samples were obtained
from Rietveld refinement and presented in Table 1. The interplanar
spacing (d value) was estimated using the relation [53,54];
1 4 ⎛ h2 + hk + k 2 ⎞ l2
= ⎜ ⎟+ 2
d 2 3⎝ a 2 ⎠ c
where h, k, and l are Miller's indices.
Volume of hexagonal close packed unit cell was calculated with the
help of following equation [53,54];
3 2
V= a c = 0.866 a2c
2
The c/a ratio, internal parameter u and degree of distortion R have
been also provided in Table 1. ZnO wurtzite structure comprises two
Fig. 1. Rietveld refinement profiles of XRD data of the Zn1-2xFexCoxO (x=0 and 0.01)
samples. The red circles represent the observed data while the solid black line through
the circles shows the calculated profile, vertical green ticks below curves indicate allowed
Bragg-reflections for the wurtzite phase. The difference pattern of the observed data and
calculated profile (blue line) is provided below Bragg reflections. (For interpretation of
the references to color in this figure legend, the reader is referred to the web version of
this article.).
D. Sharma, R. Jha Ceramics International 43 (2017) 8488–8496

Table 1
Analysed values of lattice parameters, interplanar spacing, bond lengths, bond angles,
density, and volume of unit cell for Zn1-2xFexCoxO samples.

Parameters Sample A Sample B

a (Å) 3.2492 3.2516

c (Å) 5.2051 5.2091
c/a 1.6020 1.6020
U 0.3799 0.3799
R 1.0194 1.0193
d (100) 2.8139 2.8160
d (002) 2.6026 2.6046
d (101) 2.4754 2.4772
“b” dZn-O (Å) 1.9774 1.9789
“b1” 1.9774 1.9789
α (Oa-Zn-Ob) (deg.) 108.4311 108.4330
β (Ob-Zn-Ob) (deg.) 110.4910 110.4892
d (gm-cm−3) 5.780 5.966
Fig. 2. Williamson-Hall (W-H) plot (βcosθ vs. 4sinθ) of the Zn1-2xFexCoxO (x=0 and
V (Å3) 47.5894 47.6959
0.01) samples to estimate the crystallite size ‘D’ (from intercept) and average lattice
strain ‘ε’ (from slope). The red squares represent data for sample A (ZnO) while the blue
circles show data for sample B (Zn0.98Fe0.01Co0.01O).
interpenetrating hexagonal close packed sub-lattices with a and c
lattice parameters. The degree of distortion R was calculated using
a and (101), the uniform tensile strain has been produced due to change
relation R = 8 c . Ideal wurtzite structure has value of R=1, since c/a
3 in bond length and bond angle.
ratio is 8
. The internal parameter u is ratio between the nearest The crystallite size ‘D’ of the prepared samples was obtained from
3
neighbour distance (anion-cation bond length) and lattice parameter c. Debye-Scherrer's formula [54,60];
It was calculated using following formula [55,56]; Kλ
D=
1 a2 1 β cosθ
u= +
3 c2 4 where K is Scherrer constant (K=0.9 for spherical symmetry), λ denotes
Bond length and bond angle were calculated from Rietveld refine- wavelength of XRD radiation used (λ=1.5406 Å), θ is the Bragg angle
ment (Table 1). These parameters were also calculated using following and β represents the full width at half maximum (FWHM).
formulae [55,56]; Average crystallite size ‘D’ and lattice strain ‘ε’ were also calculated
from Williamson-Hall (W-H) plot by using equation [53];
b = uc
Kλ
βhkl cosθ = 4εsinθ +
1 2 ⎛1 ⎞2 D
b1 = a + ⎜ − u⎟ c 2
3 ⎝2 ⎠ In Fig. 2, (βcosθ) was plotted on the y-axis with respect to (4sinθ)
on the x-axis. ‘D’ and ‘ε’ were calculated from intercept and slope of the
⎡⎛ ⎞−1⎤
π ⎢ ⎛ c ⎞2 ⎛ 1⎞
2
⎥ linear fit of data, respectively and given in Table 2.
α = + arccos⎢⎜⎜ 1 + 3 ⎜ ⎟ ⎜ −u + ⎟ ⎟⎟ ⎥ These parameters (‘D’ and ‘ε’) were also estimated from ‘size-strain
2 ⎢⎣⎝ ⎝a⎠ ⎝ 2⎠ ⎠ ⎥
⎦ plot’ by using the following relation [61];
⎡⎛ 2⎞ ⎤ ⎛ dhklβ cosθ ⎞2 Kλ ⎛ dhkl β cosθ ⎞ ⎛ ε ⎞
−1 2 2
⎢ 4 ⎛ c ⎞2 ⎛ 1⎞ ⎥ ⎜ ⎟ = ⎜ ⎟ ⎜ ⎟
β = 2arcsin⎢⎜⎜ +4 ⎜ ⎟ ⎜ −u + ⎟ ⎟⎟ ⎥
+
⎝ λ ⎠ D⎝ λ2 ⎠ ⎝2⎠
⎢⎣⎝ 3 ⎝a⎠ ⎝ 2⎠ ⎠ ⎥
⎦
where, dhkl is interplanar spacing for (h, k, and l) plane. Fig. 3
where, b is nearest neighbour bond length along c direction whereas b1 represents the plot of (dhkl β cosθ/λ)2 vs. (dhkl2 β cosθ/λ2). The average
represents off c-axis bond length between anion and cation atoms. crystallite ‘D’ and average lattice strain ‘ε’ were calculated from slope
Bond angles α and β are average basal bond length (Oa-Zn-Ob) and and intercept of the linear fit of data, respectively (Table 2).
average base apex angle (Ob-Zn-Ob) respectively where Oa refers O It is observed that crystallite size decreases with Fe, Co doping
atom at the apex and Ob represents O atom at the base of the concentration. The decrease in crystallite size is attributed to the
tetrahedral structure. slightly larger ionic radius of Fe2+(0.63 Å) than Zn2+(0.60 Å). The
The obtained data reveal increase in lattice parameters a and c with average lattice strain increases in Fe/Co co-doped ZnO samples than
doping of Fe/Co ion concentrations whereas values of c/a, u and R pure ZnO nanocrystals. The increase in lattice parameters, unit cell
remain constant with doping of transition metal ions. In tetrahedral volume and a decrease in crystallite size may be ascribed to the intra
arrangement, the ionic radii of Zn2+, Co2+, Fe+2 and Fe3+ are 0.60, and inter nucleating forces during the crystallization of ZnO with the
0.58, 0.63 and 0.49 Å, respectively [57,58]. Increase in lattice para- addition of Fe/Co ion concentration [62].
meters with doping is attributed to the small difference in ionic radius
of Fe2+(0.63 Å) and host atom Zn2+(0.60 Å). However, the presence of Table 2
Fe3+ energy state is not completely ruled out without any further Calculated crystallite size and average lattice strain for Zn1-2xFexCoxO samples.
characterization and study. The unit cell volume of samples A and B are
Sample Crystallite Size (nm) Strain
increased with doping concentration because of increased lattice
parameters. Fe/Co ions have been successfully substituted the Zn ion Scherrer Size- W-H Plot Size-Strain Plot W-H Plot
sites within host lattice following the Vegard's law [59]. The d-values of Formula Strain
(100), (002) and (101) are increased with doping of Fe/Co concentra- Plot
tion which is due to change in bond length and bond angles. The strain
Sample A 40.41 43.19 46.01 2.3757×10−3 2.9594×10−4
produced in the lattice is responsible for the change in interplanar Sample B 31.91 35.00 37.48 3.0531×10−3 3.9408×10−4
spacing [53]. In the perpendicular direction of the plane (100), (002)

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D. Sharma, R. Jha
Fig. 3. Size-strain plot of the Zn1-2xFexCoxO (x=0 and 0.01) samples to estimate the
crystallite size ‘D’ (from slope) and average lattice strain ‘ε’ (from intercept). The values
of (dhkl β cosθ /λ)2 are plotted against (dhkl2 β cosθ /λ2). The red squares represent data
for sample A (ZnO) while the blue circles show data for sample B (Zn0.98Fe0.01Co0.01O).
(For interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.).
3.2. Electron microscopic study
The morphology of pure and doped ZnO sample was examined
using SEM. Fig. 4 represents the SEM images of sample A and sample
B. SEM images reveal spherical shape of prepared samples. In both
samples, the particle size is found less than 50 nm. These nanoparticles
show almost uniform size distribution and grain boundaries with small
agglomeration. A closer study of SEM images suggests that particle size
for sample B is less than that with the sample A, which is in good
agreement with XRD results.
TEM was used to further study the morphology of
Zn0.98Fe0.01Co0.01O sample. Fig. 5 shows the typical TEM, SAED
images of Fe/Co doped ZnO nanoparticles. In a study of TEM images,
it has been observed that most of the nanoparticles are spherical in
shape with smooth surfaces. TEM images show the clear and well-
defined grain boundaries and free state for synthesized nanoparticles.
According to Straumal et al. [63], these grain boundaries and the free
state may affect the physical characteristics of the sample. The particle
size estimated from TEM images corroborates with the size calculated
from XRD analysis.
SAED pattern of Zn0.98Fe0.01Co0.01O sample is indexed and shown
in the inset of Fig. 5 which represents the polycrystalline nature of
prepared sample. Obtained d values from SAED pattern confirm the
wurtzite structure of the sample. Detailed analysis of XRD patterns and
TEM measurements suggests the incorporation of Fe/Co ions into the
host lattice of ZnO.
Fig. 4. SEM image of sample A (pure ZnO) and sample B (Zn0.98Fe0.01Co0.01O).
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Ceramics International 43 (2017) 8488–8496
3.3. Fourier transform infrared spectroscopy
Fourier transform infrared spectroscopy (FTIR) provides the in-
formation related to functional groups present in the sample, the
molecular geometry, and intra or inter-molecular interactions. In this
study, FTIR was used to study the vibrational mode of the samples A
and B. FTIR spectra of samples are shown in Fig. 6. The band
frequencies below 800 cm−1 are generally because of the bond between
inorganic elements. All observed band frequencies for sample A and
sample B are provided in Table 3. The prominent bands are observed at
around 428 and 419 cm−1 for the pure and doped sample, respectively,
due to the stretching vibration of Zn-O bond in tetrahedral coordina-
tion. The bands at around 672 cm−1v are very weak bands assigned to
the stretching vibrations of Zn-O bonds in octahedral arrangements.
The tetrahedral co-ordinations are much more prevalent and stronger
than the octahedral coordinations in the prepared samples. Therefore,
it further confirms the wurtzite structure of samples [64,65]. The weak
band at around 672 cm−1 suggests that Fe/Co ion doping do not affect
band related to octahedral coordinations. Therefore, Fe/Co ions are
substituted only at tetrahedral arrangement instead of octahedral
coordination in ZnO.
Band frequencies at around 1384, 1386 cm−1 are assigned to the
asymmetric stretching vibrations of C˭O group due to Lewis acidity.
While the band at around 1591, 1581 cm−1 are attributed to the
symmetric stretching vibrations of C˭O group because of Bronsted
acidity.
CO2 molecules present in alcohol and in the air are responsible for
2345 and 2346 cm−1 bands. The band frequencies at around 2855,
2854 cm−1 and 2926, 2925 cm−1 are reflected due to C-H bond bending
and C-H bond stretching, respectively. Such bands are not considered
as contamination in samples [65]. These vibrational bands represent
the presence of absorbed groups on the surface of nanocrystals. In
FTIR, broad absorption peaks at around 3455 and 3457 cm−1 are
ascribed to –OH group due to H2O which shows the existence of water
molecules adsorbed on the surface of nanoparticles. The Fe/Co co-
doped ZnO sample can be easily dispersed into nonpolar and polar
solvents because of surface hydroxyl groups. These surface hydroxyl
groups are helpful in providing functional groups which can react with
functional organic molecules (dye, cluster compounds etc) or quantum
dots (Cd or Pb chalcogenides, green quantum dots, alloy quantum dots
etc) with optoelectronic properties for fabrication of effective junction
devices (e.g. dye-sensitized solar cells, quantum dot sensitized solar
cells, organic solar cells and perovskite solar cells) [65,66].
3.4. UV–Visible spectroscopy
Room temperature UV–Visible spectra were recorded by dispersing
prepared nanocrystals in DI water and using DI water as the reference.
The obtained absorption spectra for sample A and sample B are shown
in Fig. 7. The absorption peaks are observed at around 378 and 383 nm
D. Sharma, R. Jha Ceramics International 43 (2017) 8488–8496

Fig. 5. TEM images of Zn0.98Fe0.01Co0.01O nanocrystals. Inset of image A shows the indexed SAED pattern for Zn0.98Fe0.01Co0.01O nanocrystals (sample B).

Fig. 7. Absorption spectra (UV–Visible) of the Zn1-2xFexCoxO (x=0 and 0.01) samples.
(For interpretation of the references to color in this figure, the reader is referred to the
web version of this article.).
Fig. 6. FTIR spectra of the Zn1-2xFexCoxO (x=0 and 0.01) samples representing wurtzite
structure and other functional groups. (For interpretation of the references to color in
this figure, the reader is referred to the web version of this article.). Table 4
Absorption data for sample A and B.

Table 3 Parameters Sample A Sample B

FTIR data of different vibrational modes of Zn1-2xFexCoxO samples.
Absorption wavelength, λ (nm) 378 383
Sample A Sample B Modes (cm−1) Optical band gap, Eg (eV) 3.283 3.240

428 419 Zn–O bond (tetrahedral)

672 672 Zn–O bond (octahedral)
exchange interaction between the band electrons of ZnO (in valence
881 880 ethanol precursor
1384 1386 Asymmetric stretching of C˭O and conduction band) and the localized d electrons of the Fe & Co ions
1591 1581 Symmetric stretching of C˭O substituting for Zn2+ ions [68]. The strong exchange interaction (s-d
2345 2346 CO2 molecules in air and p-d) result into a positive and negative correction to the valence
2855 2854 C–H bond bending
and conduction band edges, respectively, which might be possible
2926 2925 C–H bond stretching
3455 3457 O–H bond
cause of shrinkage of the band gap in the doped sample [69]. In our
study, the observed crystallite sizes are much larger than Bohr exciton
radius of ZnO. Therefore, the quantum confinement effect cannot be
responsible for the observed change in the band gap of samples. The
for sample A and B, respectively. The optical energy band gaps were structural changes play an important role for significant change in the
calculated using these absorption peaks (Table 4). The band gap for band gap with Fe/Co ions doping concentrations in ZnO.
pure ZnO is found up to 3.28 eV which is slightly less than the band gap
of bulk ZnO material (3.31 eV). Such change in the band gap of pure
ZnO is due to the presence of oxygen vacancies or/and defects at the 3.5. PL spectroscopy
surface of ZnO nanocrystals [67]. In FTIR study of pure ZnO sample,
the –OH surface groups are found which is an effective n-type defect in PL spectroscopy is a non-destructive sensitive technique which is
ZnO. used to study the optical properties of the sample. PL spectroscopy
In sample A and B, the estimated optical band gap is decreased with provides information about the energy states of defects and impurities
Fe/Co doping ZnO lattice. Beltrán et al. [38] found similar observations which are helpful to understand the structural defects in semiconduc-
i.e. decrease in band gap with increasing concentrations of Fe/Co ions tor samples. Fig. 8 shows the room temperature PL spectra measured
in ZnO. The decrease in band gap is attributed to stronger sp-d by exciting the nanocrystalline samples at 320 nm. Fig. 9 represents

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D. Sharma, R. Jha Ceramics International 43 (2017) 8488–8496

Fig. 8. Room temperature PL spectra of the Zn1-2xFexCoxO (x=0 and 0.01) samples. (For
interpretation of the references to color in this figure, the reader is referred to the web
version of this article.).
Fig. 9. De-convoluted PL spectra of the Zn1-2xFexCoxO (x=0 and 0.01) samples.
de-convoluted PL spectra which are obtained by multiple peaks fitting
of PL spectra using Gaussian function. In both the samples, PL peaks
are broad which may be possible due to the presence of defects and
several recombination sites. The asymmetric nature of obtained PL
spectra is attributed to the presence of other inherent emission peaks
due to distributed defect states in the interior and on the surface of
nanocrystals. In PL spectra, the defects related emissions dominate
over the near band edge emission of ZnO. Therefore, the near band
edge emission of ZnO at around 387 nm is weakly resolved.
The PL spectra have five peaks originating around 387, 413, 435,
473 and 515 nm. The first peak corresponds to the ultraviolet region.
Other four peaks relate to violet, violet-blue, blue-green and green in
the visible region, respectively. The intensity of emission peaks is
varied with Fe/Co ions doping concentration (Table 5). A slight shift in
emission peaks towards higher wavelength is observed with doping of
Fe/Co ions in ZnO. The peak in UV region is ascribed to the near band
edge emission. The energy corresponds to this peak is approximately
equal to the band gap of sample calculated using UV–Vis measurement
[70]. The UV emission peak is reflected possibly due to radiative
recombination of free excitons through an exciton-exciton collision
process [71,72].
The violet emission around 413 nm is related to zinc vacancies
since the energy interval between the zinc vacancy (VZn) level and the
bottom of the conduction band is approximately 3.00 eV. The energy
interval between the valence band and the interstitial Zn level (Zni)
(~2.85 eV) is consistent with our observation of violet-blue emission
around 435 nm. Shi et al. [73] and Kumar et al. [4] observed the violet-
blue emission possibly due to radiative defects related to trapping
states existing at grain boundaries. In our study, the emission at
435 nm originates because of radiative transition between the valence
band and this level related to traps at grain boundaries. The presence of
emission peak corresponding to the blue-green band (~473 nm) is
attributed to the surface defects [74]. The green band emission
(~515 nm) is originated due to recombination of electrons with holes
trapped in singly ionized oxygen vacancies [75].
In Fe/Co ions co-doped ZnO sample, the emission intensities of
violet and violet-blue color in the visible region are slightly decreased.
The Fe/Co ions in ZnO play a role as quenching center to suppress the
radiative recombination transitions and to increase non-radiative
recombination processes [76]. The non-radiative transition occurs
when free electron recombines through Fe or Co ion impurity level
rather than populating donor-acceptor pairs. It may also be ascribed to
energy transfer processes from donor-acceptor pairs to neighbouring
Fe or Co ions in ZnO lattice [77,78]. The Fe/Co ions co-doped ZnO has
increased distortion centres and surface defects as compared to pure
ZnO nanocrystals.
Intensities of blue-green and green color emission are increased
with Fe/Co co-doping concentration in ZnO nanocrystals. The increase
in green color emission reveals the increased oxygen vacancies related
defects in doped ZnO sample.
In the de-convoluted PL spectra, fitted Gaussian peaks are not only
having varying intensity but also have varying peak width. To analyse
the defect states, areas of emission peaks are also an important factor
to be considered apart from intensity of peak [79]. The color fraction PC
is calculated for each color using the relation PC=AC/AT where, AC is
the area of fitted peak and AT is the total area bounded by the full PL
spectra. It relatively estimates the different defect state. A normalized
color fraction PN is also determined for the each color using PN=PC/PUV
by considering the UV emission normalized to 1. The values of
intensities of individual peaks, IC/IUV, PDLE/PNBE, PC and PN are
provided in Table 5. Value of PDLE/PNBE reveals that deep level
emission (DLE) is largely increased as compared the near band edge
emission (NBE) in Fe/Co co-doped ZnO sample. The relative color
intensity IC/IUV is increased for each color with Fe/Co doping

Table 5
Data analysed from de-convoluted PL spectra for sample A (pure ZnO) and sample B (Zn0.98Fe0.01Co0.01O).

Name Peak λ (nm) E (eV) I A Pc PN IC/IUV PDLE/PNBE

Sample A UV 387.5 3.20 235.50 3201.29 0.1037 1.0000 1.0000 8.6431

Violet 413.5 3.00 267.38 6056.16 0.1962 1.8918 1.1354
Violet-Blue 435.5 2.85 211.33 6274.70 0.2033 1.9601 0.8973
Blue-Green 473.5 2.62 192.73 6758.61 0.2189 2.1112 0.8184
Green 515.5 2.41 227.56 8579.50 0.2779 2.6800 0.9663

Sample B UV 387.5 3.20 105.79 1501.12 0.0634 1.0000 1.0000 14.7709

Violet 418.0 2.97 220.56 3750.94 0.1584 2.4988 2.0849
Violet-Blue 445.0 2.79 186.03 4200.53 0.1774 2.7983 1.7586
Blue-Green 475.5 2.61 208.26 5932.40 0.2506 3.9520 1.9687
Green 515.0 2.41 229.33 8288.99 0.3501 5.5219 2.1678

8493
D. Sharma, R. Jha
Fig. 10. Room-temperature M-H plot of the Zn0.98Fe0.01Co0.01O sample. Inset (i)
represents M-H curve for pure ZnO at room temperature while inset (ii) shows zoomed
M-H curve of the Zn0.98Fe0.01Co0.01O nanocrystals.
concentration. Relatively large value of IC/IUV for green color in doped
ZnO sample shows the increase in oxygen vacancies. PC and PN have
larger values (especially in case of green color emission) for Fe/Co co-
doped ZnO sample than that of pure ZnO nanocrystals.
On the basis of above discussion, it is concluded that there are large
number of oxygen defect state in doped ZnO sample. The singly
occupied oxygen point defects play a key role to induce RTFM in
doped ZnO sample when associated with BMPs.
3.6. Magnetic measurements
RTFM in TM-doped oxide DMSs is the salient behaviour for its
practical applications. The M-H curves of pure ZnO and Fe/Co ion co-
doped ZnO sample are shown in Fig. 10. Pure ZnO nanocrystals show
obvious diamagnetic behaviour. Fe/Co ion-doped ZnO nanoparticles
exhibit the room-temperature ferromagnetic behaviour. In inset (II) of
Fig. 10, the zoomed M-H curve of Fe/Co ion-doped ZnO nanoparticles
is presented. Such observed hysteresis loop at room temperature
reveals that sample B is weakly ferromagnetic and does not show
superparamagnetic behaviour.
In literature, origin of RTFM is explained through various extrinsic
(due to the formation of clusters or secondary phases of dopant ions)
and intrinsic (due to various exchange interactions) mechanisms. The
magnetic ion impurities may be responsible for observed ferromagnet-
ism. The formation of Fe and/or Co ion related secondary phase may
also be cause for RTFM in DMS. Ferromagnetic behaviour may be
attributed extended defects in the nanoparticles. Transition metal (Fe
and/or Co) precipitation may contribute in ferromagnetic nature of
doped oxide samples. There is a possible formation of FeO/Fe2O3 and/
or CoO phase in doped ZnO nanocrystals which can be the reason of
observed RTFM behaviour of the sample.
In our study, the formation of FeO/Fe2O3 and/or CoO phase in Fe/
Co ion-doped ZnO lattice structure can be ruled out since these phases
have not been observed in prepared nanocrystals. XRD analysis
confirms no evidence of metallic Fe and/or Co clusters and Fe, Co
related secondary phase, therefore it cannot be a source of observed RT
ferromagnetism.
In our experiment, both the samples were synthesized under
identical reaction conditions. Therefore impurities cannot be respon-
sible for observed magnetization in sample B. XRD, TEM and FTIR
spectroscopic study reveal successful incorporation of Fe/Co ions at the
Zn sites in ZnO wurtzite structure.
Grain boundaries play a key role in deciding the ferromagnetic
behaviour of ZnO nanocrystals. To investigate the role of defects and
8494
Ceramics International 43 (2017) 8488–8496
grain boundary, Straumal et al. [17,21,63,80–82] introduced the grain
boundary specific area SGB, the ratio of the grain boundary area to the
volume. They studied the effect of grains on the magnetic character-
istics of Co, Mn, Fe and Ni doped ZnO nanocrystals. The study includes
the SGB for single crystalline and polycrystalline ZnO along with
different shape and dense network of grains. The SGB can be calculated
using the relation SGB=1.65/D for polycrystals, where D is the average
crystallite size. Straumal et al. [17,21,63,80–82] showed that the ZnO
samples are ferromagnetic only if SGB exceeds a threshold value of
grain boundary specific area Sth. The values of Sth for Fe doped and Co
doped ZnO nanocrystals are 3×104 m2 m−3 and 1.5×106 m2 m−3,
respectively [17]. In our experimental study of Fe and Co co-doped
ZnO lattice structure, the SGB is 47.14×106 m2 m−3 which is much
larger than Sth for Fe doped and Co doped ZnO nanocrystals.
Therefore, we believe that observed RTFM for Fe and Co co-doped
ZnO is due to the combined effect of grain boundaries and intrinsic
exchange interaction of magnetic moments of Fe and/or Co ions.
According to Straumal et al. [17], the Sth is 5.3×107 m2 m−3 for
ferromagnetic ordering in case of pure ZnO nanocrystals. In our study,
the Sth is found to be 3.82×107 m2 m−3 for pure ZnO which is less than
threshold value for grain boundary specific area. Therefore, grain
boundaries did not induce the ferromagnetic behaviour in pure ZnO
nano-crystals.
The intrinsic ferromagnetism is a debatable issue in the metal
oxide. It is discussed through different theories e.g. (i) RKKY theory in
which the localized magnetic moments interact with each other
through charge carriers (i.e. local spin-polarized electrons and free
carriers), (ii) the double exchange mechanism [16] or superexchange
mechanism, and (iii) the donor impurity band exchange model.
The RKKY interaction theory is based on conduction electrons (free
charge carriers). In our experiment, ZnO has not such free carriers with
such a low doping of Fe/Co ions. Therefore, RKKY interaction does not
provide solid ground for observed FM.
Double exchange mechanism is direct exchange interaction in
which magnetic ions in different charge states (d state of Fe and/or
Co ions) interact with each other through virtual hopping off the extra
electron from one ion to the other via interaction with p-orbital
whereas, super-exchange interaction (an indirect interaction) is me-
chanism between non-neighbouring magnetic ions [83–85]. Park et al.
[46] suggested no tendency of charge transfer between Fe/Co ions,
although concentrations of Fe/Co were greater than 6%. In our study,
concentrations of magnetic cations are very low, therefore double
exchange or superexchange interactions are not responsible factors for
FM behaviour of sample B. In donor impurity band exchange model,
FM is attributed to indirect exchange interaction through shallow
donor electrons which form bound magnetic polarons (BMP) [86,87].
In the present experiment, magnetic ions, carriers, and/or defects can
collectively result into BMPs which may contribute to RTFM behaviour.
In PL analysis, oxygen vacancies exist in prepared nanocrystals which
also play a crucial role in magnetic properties of doped sample.
Here, it is concluded that the combined effect of the grain
boundaries (extrinsic interaction) and oxygen vacancies associated to
BMPs (intrinsic exchange interaction) is responsible for the observed
RTFM behaviour of Fe/Co ions doped ZnO sample.
4. Conclusions
Pure ZnO and Fe/Co co-doped ZnO nanoparticles were synthesized
using co-precipitation method. The structural, optical and magnetic
properties of prepared samples were studied in detail using XRD, SEM,
TEM, FTIR, UV–Vis, PL spectroscopy and magnetic measurement
(VSM). The Rietveld analysis of XRD profiles and FTIR study showed
the single phase, hexagonal wurtzite structure for prepared samples.
FTIR confirmed the tetrahedral coordination of the oxygen ions
surrounding the Zn ions and vice versa. SEM and TEM revealed the
spherical morphologies of prepared sample with well defined grain
D. Sharma, R. Jha
boundaries. Decrease in optical band gap with Fe/Co doping in ZnO is
interpreted as stronger sp-d exchange interaction between the band
electrons of ZnO (in valence and conduction band) and the localized d
electrons of the Fe & Co ions substituting for Zn2+ ions. PL measure-
ments showed the UV emission (NBE), violet, violet-blue, blue-green
and green emissions in the visible region. Detailed analysis of de-
convoluted PL spectra revealed that Fe and Co ions in ZnO lattice
increased the amount of oxygen vacancies and other defect states.
Observed RTFM behaviour in Fe/Co co-doped ZnO nanocrystals is due
to the grain boundaries and oxygen vacancies associated to BMPs.
Results of this experimental study enhance the understanding of
structural, magnetic and optical properties in Fe/Co co-doped ZnO
nanocrystals.
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