Journal of Rare Earths 39 (2021) 1224e1231

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Journal of Rare Earths

journal homepage: http://www.journals.elsevier.com/journal-of-rare-earths

Influence of Y3þ, Yb3þ, Gd3þ cations on structural and electromagnetic

properties of CuFe2O4 nanoferrites prepared via one step sol-gel
method
Aleena Kiran a, Majid Niaz Akhtar b, *, Muhammad Yousaf c, Khalid Mujassam Batoo d,
Omar M. Aldossary e, Salman Naeem Khan f
a
Department of Physics, COMSATS University Islamabad, Lahore Campus, Defence Road Off Raiwind, Lahore, 54000, Pakistan
b
Department of Physics, Mohammad Nawaz Sharif University of Engineering and Technology, Multan, 60000, Pakistan
c
School of Energy and Environment, Southeast University, No.2 Si Pai Lou, Nanjing 210096, China
d
King Abdullah Institute for Nanotechnology, King Saud University, P.O. Box 2455, Riyadh, 11458, Saudi Arabia
e
Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box-2455, Riyadh, 11451, Saudi Arabia
f
Micro-mm Wave Laboratory (M2L), Department of Physics, COMSATS University Islamabad, Lahore Campus, Defence Road Off Raiwind, Lahore, 54000,
Pakistan

a r t i c l e i n f o a b s t r a c t

Article history: Rare earths (REs) play a key role in distorting spinel structure by creating some defects at the lattice sites
Received 5 June 2020 and make them suitable for magnetodielectric applications. In the present study, the nanoferrites of
Received in revised form CuRE0.02Fe1.98O4, where REs ¼ Y3þ, Yb3þ, Gd3þ, were prepared using one step solegel method. The
13 November 2020
prepared samples are copper ferrite (CFO), yttrium doped copper ferrite (Y-CFO), ytterbium doped
Accepted 7 December 2020
Available online 15 December 2020
copper ferrite (Yb-CFO) and gadolinium doped copper ferrite (Gd-CFO), respectively. The single-phase
structure of all the REs doped nanoferrites was determined by X-ray diffraction (XRD) analysis. The
porosity, agglomerations and grain size of the REs doped copper ferrite were examined using field
Keywords:
Rare earth elements
emission scanning electron microscopy (FESEM) analysis. Fourier transform infrared spectroscopy (FTIR)
Nanoparticles elaborates the phase formation and environmental effects on the REs doped nanoparticles (NPs). The
Spinel ferrites recorded room temperature MH loops from a vibrating sample magnetometer (VSM) elucidate the
VSM magnetic properties of the REs doped spinel nanoferrites. The magnetic saturation (Ms) was calculated in
VNA the range of 23.08 to 51.78 emu/g. The calculated coercivity values (272.6 to 705.60 Oe) confirm the soft
Magnetodielectric applications magnetic behavior of REs doped copper ferrites. Furthermore, the electromagnetic and dielectric prop-
erties were assessed using a Vector network analyzer (VNA) from 1 to 6 GHz. The permeability,
permittivity, dielectric tangent loss and electric modulus of the REs doped spinel ferrites illustrate that
the prepared NPs may be suitable for microwave and high frequency applications.
© 2020 Chinese Society of Rare Earths. Published by Elsevier B.V. All rights reserved.

1. Introduction
The demand of advanced ferromagnetic materials has been
increased by improving their magnetoelectric and magnetodi-
electric properties for electronic and communication applications.1
The magnetic materials doped with REs metal ions play a key role in
enhancing characteristics of the ferromagnetic materials by con-
structing novel and multifunctional devices and enabling them to
* Corresponding author.
E-mail addresses: majidniazakhtar@gmail.com, majidniazakhtar@mnsuet.edu.
pk (M.N. Akhtar).
be used for radio frequency (RF), antennas and microwave radi-
ations.2e5 Copper ferrite (CuFe2O4) is a highly emerging material in
spinel ferrite family because of their phase transition and semi-
conducting nature.6 CuFe2O4 attained the researchers’ attention
from the last few years due to its multiple features such as single-
phase cubic crystalline structure and high electronic conduction
which are suitable for dielectric applications.7,8 The cubic crystal-
line structure possesses two interstitial (tetrahedral as A-site and
octahedral as B-site) sites and ion’s distribution on its interstitial
sites enables the broad variations in spinel properties.9,10 The
chemical formula of the spinel ferrite is MFe2O4, where M denotes
divalent ions such as Cu2þ, Co2þ, Mn2þ, Zn2þ and Ni2þ.11 The
different metal cations accommodated in the interstitial sites (A-

https://doi.org/10.1016/j.jre.2020.12.003
1002-0721/© 2020 Chinese Society of Rare Earths. Published by Elsevier B.V. All rights reserved.
A. Kiran, M.N. Akhtar, M. Yousaf, et al. Journal of Rare Earths 39 (2021) 1224e1231

site, B-site) and trivalent metal ions such as Al3þ, Cr3þ and Ga3þ are 2.1. Characterizations of REs doped Cu ferrite
incorporated in place of Fe3þ ions.12 Moreover, the physical prop-
erties also depend on the methodology, sintering conditions, The cubic crystalline structure and phase were studied using an
chemical stability and controlled grain size.13 CuFe2O4 belongs to X-ray diffractometer (D8 Advance Bruker). Morphology, agglom-
soft ferrite family with inverse spinel structure. In inverse spinel erations and grain size of the as-prepared samples were analyzed
structure, rare earths cations and half of Fe3þ ions occupy B-site by a field emission scanning electron microscope (FESEM). Fourier
whereas other half Fe3þ ions are distributed at A-sites.14,15 There- transform infrared spectroscopy (FTIR) was employed in the range
fore, most of the lattice sites exist for the cation movements and of 400e4000 cm1 to study the chemical composition, absorbing
their distribution at the interstitial sites.16 The inverse spinel bands and metal ion stretching. The magnetic properties of the
structure of CuFe2O4 is significant because of its large coercivity and synthesized samples were captured using a vibrating sample
large saturation magnetization.17 REs doped copper ferrite is suit- magnetometer (VSM). The permittivity, permeability and scat-
able for magnetic recording, digital recording disks RAMs and mi- tering parameters were extracted by a Vector network analyzer
crowave absorption applications.18 (VNA) using coaxial cell in frequency range of 1e6 GHz.
The significant effects on the spinel ferrite properties were
noticed by the doping of REs metal ions.19,20 REs metal ions dopant
3. Results and discussion
enhanced the absorbing properties in microwave devices by
improving magnetization and lower dielectric losses.21e24 The ionic
3.1. Phase and microstructure analysis
radii of REs cations are larger than those of Cu2þ, Fe3þ ions and their
cation distribution on the spinel lattice makes them suitable for
XRD patterns of the REs doped Cu ferrite are depicted in Fig. 1.
altering the dielectric characteristics. Kanna et al.25 worked on
The sharp peaks of the samples show single phase structure of the
MneCu doped with Dy3þ and reported less dielectric losses with
nanoparticles (NPs). The higher intensity peak at 35.93 clearly
the doping of rare earth cations. Elayakumar et al.26 reported
shows the existence of spinel phase with cubic structure. Lattice
cerium doped CuFe2O4 and observed the influence of rare earth
constant and cubic crystalline peaks are further confirmed by ICDD
(Ce3þ) behavior on the saturation magnetization and antibacterial
#00-08-0234 card and Scherrer’s formula was used to find the
activity. Naresh et al.27 analyzed lanthanum doped copper ferrite in
crystallite size of the NPs.28 The average crystallite size of the
the presence of barium and noticed the super paramagnetic nature.
prepared NPs is 30.08e42.20 nm, respectively. The variations in the
The coercivity was increased by the doping of lanthanum from 54 G
peak’s intensities are also observed in the prepared samples due to
to 180 G respectively. The prepared NPs can be used for techno-
the migration of REs cations and Fe3þ ions at octahedral and
logical applications such as opto-electric devices or biomedical
tetrahedral sites. REs cations in Cu ferrite show the variations
applications.
which is due to the larger ionic radii of rare-earths ions than those
Inspired by the previous reported work, REs doped CuFe2O4 NPs
of Cu (0.074 nm) and Fe3þ (0.069 nm) ions, respectively. Table 1 lists
were prepared using one step solegel combustion approach. The
the lattice parameter, FWHM, d-spacing and crystallite size of the
REs metal ions (Y3þ, Yb3þ, Gd3þ) were substituted to analyze the
NPs. The lattice constant shows variations which may be because of
structural, morphological, phase formation and dielectric effects.
the different ionic radii of the REs cations.29 REs cations are sig-
XRD, FESEM, FTIR, VSM and VNA were used to evaluate the struc-
nificant to deform the spinel structure by the generation of stress,
tural, morphological, optical and magnetoelectric properties of the
which may be caused by the expansion in the lattice sites.30,31
RE (Y3þ, Yb3þ, Gd3þ) doped CuFe2O4.
Moreover, equally distributed REs cations at octahedral sites and
overlapping of Fe3þ ions with REs create the distortion in the spinel
2. Experimental
structure.32 Yousaf et al.33 explained the variations of structural
parameters of spinel ferrite NPs by the doping of different REs
Copper nitrate [Cu(NO3)3,9H2O] (Sigma, 99.9%), iron nitrate
cations. In addition, the decreasing trend in micro strain is the
[Fe(NO3)3,9H2O] (Sigma 99.9), yttrium nitrate [Y(NO3)3,6H2O]
confirmation of the actual single-phase cubic structure of the spinel
(Sigma 99.9%), cerium nitrate [Ce(NO3)3,6H2O] (Sigma 99.9%),
ferrite NPs.34 The internal structural parameters of the spinel ferrite
ytterbium nitrate [Yb(NO3)3,6H2O] (Sigma 99.9%), praseodymium
nitrate [Pr(NO3)3,6H2O] (Sigma 99.9%), gadolinium nitrate
[Gd(NO3)3,6H2O)] (Sigma 99.9%) and citric acid [(C6H8O7)] (Sigma
99.9%) were used as a precursor to prepare the NPs of REs doped
copper ferrite. The stoichiometric amounts of metallic nitrates were
separately liquified in 100 mL deionized (DI) water. Moreover, all
the prepared solutions for each composition were mixed into a
beaker and placed on a magnetic stirrer. The temperature was
increased from 25 to 75  C to follow the solegel procedure. Citric
acid (C6H8O7) was dissolved with continuous stirring to prepare a
homogenous solution for 30 min and further mixed with nitrate
solution. Ammonia (NH3) solution was continuously added drop-
wise until the pH reached at 7. The prepared solution was changed
into gel after few hours and then gel was combusted at 110  C by
obtaining fluffy loose powder. The dried ashes were ground using a
mortar and a pestle, and placed in a muffle furnace at 800  C for 5 h
for sintering purpose. The obtained fine powders were proceeded
for further assessments to analyze the morphological, structural,
dielectric, magnetic and electromagnetic properties. The samples
were copper ferrite (CFO), yttrium doped copper ferrite (Y-CFO),
ytterbium doped copper ferrite (Yb-CFO) and gadolinium doped
copper ferrite (Gd-CFO), respectively. Fig. 1. XRD patterns for CFO, Y-SFO, Yb-CFO and Gd-CFO spinel ferrite NPs.

1225
A. Kiran, M.N. Akhtar, M. Yousaf, et al.
Table 1
XRD parameters for CFO, Y-SFO, Yb-CFO and Gd-CFO spinel ferrite NPs.
Samples Max peak FWHM (nm) d-spacing (nm)
2q ( )
CFO 35.861 0.02259 0.25021
Y-CFO 36.251 0.02285 0.24760
Yb-CFO 36.147 0.02069 0.24829
Gd-CFO 35.315 0.02895 0.25395
NPs such as ionic radii, MO distances and their shared and un-
shared edges were also measured to evaluate the detailed internal
structural properties. The ionic radii (rA, rB) of spinel ferrite NPs at
octahedral site and tetrahedral site were also calculated.28 The
variations in ionic radii values of the prepared NPs at the lattice
sites with the doping of REs cations are listed in Table 2. The vari-
ations in ionic radii values of Cu ferrite NPs can be observed because
of the substitution of different REs elements. However, the divalent
Cu2þ and trivalent REs cations with Fe3þ ions are replaced at
tetrahedral and octahedral sites, which may cause change on the rA
and rB. The shared edges, MO distances and unshared edges of the
REs doped Cu ferrites were calculated by the relations as was
elaborated by Akhtar et al.35 The internal structural parameters of
the REs doped nanoferrites strongly depends on the calculated
lattice parameter.36 The ionic radius of A-site (rA ) and B-site (rB )
critically rely on the cation distributions at the lattice sites.
Consequently, the values of the theoretical lattice parameter are
also found to be comparable with the experimental values of the
lattice parameter.
FESEM was performed to investigate the morphology, grain size
and agglomerations in REs doped copper ferrite. FESEM images of
the prepared REs doped Cu ferrites are presented in Fig. 2. The mi-
crographs show non-uniform grain size, agglomerations and well
packed structure on the surface of copper ferrite. The agglomerations
in the spinel ferrites can be ascribed to the factors such as method of
preparation, sintering temperature and magnetic nature of the
synthesized samples.37 The average gain size of the prepared NPs is
found using the line intercept method (LIM).38 The measured grain
size of the REs doped Cu ferrite is found in the range of 0.13e0.18 mm,
respectively. The grain size shows variations which may be due to
the different REs doping contents in spinel ferrite.
3.2. Spectroscopy analysis
FTIR of the REs doped copper ferrite NPs was employed to
analyze the spectroscopy properties such as phase formation, metal
ions stretching and environmental effects. FTIR results of REs doped
copper ferrite NPs are presented in Fig. 3. The distinct absorption
bands were detected between 600 and 800 cm1 which are related
to the tetrahedral (v1-800 cm1) and octahedral site (v2-600 cm1),
respectively. In spinel ferrites, the low absorption band at 600 cm1
explains the metal ion stretching at octahedral sites, while the
higher absorption band (v2) corresponds to MO vibration at
tetrahedral sites, which depicted the evidence of the formation of
spinel structure.39 The occurrence of the same absorption bands is
the validation that REs cations are completely doped in copper
ferrite without changing metal ions stretching. The force constants
kt and ko from absorption band were also calculated from the
relation40:
kt=o ¼ 4p2 c2 v21=2 m
where, kt and ko are force constants for tetrahedral and octahedral
sites, c is a constant (3  108 m/s) and m (2.601  1023 gm) is
reduced mass of O2 and Fe3þ.
Journal of Rare Earths 39 (2021) 1224e1231
Crystalline size (nm) a (nm) ath (nm) Cell volume (nm3) Micro strain (%)
38.62 0.9362 0.9346 0.82055 0.0031
38.22 0.9264 0.9141 0.79505 0.0030
42.20 0.9290 0.9178 0.80176 0.0028
30.08 0.9501 0.9389 0.85764 0.0040
The measured values (ko and kt) of the REs doped Cu ferrites are
listed in Table 3. It is noticed that v1 is nearly constant but v2 shows
the variations because of different REs substitution. The bond
length stretching at octahedral site confirms that copper ferrite is
the inverse spinel cubic structure and it tends to occupy octahedral
site as discussed in literature.41 The small variations of eCOOH
symmetric and asymmetric stretching are also observed at
1434 and 1576 cm1, and other absorption bands at 2350 and
3410 cm1 are ascribed to the carboxyl group and NO 3 group.
3.3. Magnetic properties
Magnetic loops are used to analyze the magnetic properties of
the REs doped ferrites NPs. The magnetic loops of REs doped copper
ferrite were recorded using VSM at 15 kOe and are presented in
Fig. 4. The coercivity (Hc), magnetic moments, saturation magne-
tization (Ms), magnetic anisotropy constant and remanence (Mr) are
calculated from MH loop and are presented in Table 4. The mag-
netic parameters of the REs doped copper ferrites are different due
to the diverse ionic radii of substituted RE elements. The amount of
REs in spinel ferrite plays a key role in altering the net magnetic
moment of the prepared NPs and implemented for required ap-
plications.42 Moreover, REs elements distort the spinel ferrite
structure by being distributed at the copper ferrite lattice sites
(octahedral site, tetrahedral site).43 MH curves of the synthesized
samples illustrate that the RE doped copper ferrite material is
superparamagnetic with negligible Mr and Hc. Superparamagnetic
behavior of the REs doped Cu ferrite NPs can be ascribed to their
smaller crystallite size which makes them thermally activate to
overcome the magnetic anisotropy. The observed Ms values are
23.08e51.78 emu/g, respectively. The different behaviors of the
saturation magnetization are elucidated by the doping of different
RE elements in copper ferrite. Furthermore, ionic radii of the REs
also affect the saturation magnetization of the prepared spinel
ferrite. It is noticed that the pure copper ferrite has higher
magnetization as compared to substituted REs metal ions. The
magnetization of the spinel ferrite particles depends on the lattice
defects and surface spin disorder by applying the magnetic field.
The REs elements are important to create the defects or break the
bonds in spinel ferrite structure, which further allows magnetic
moments of Fe3þ ions for random orientation.44 Therefore, net
magnetization of REs doped metal ions exhibits decreasing trend as
compared to pure CFO NPs. Bohr magneton was calculated as
follows40:
Ms  Mw
mB ¼ (2)
5585
where, Ms is the saturation magnetization and Mw is the molecular
(1) weight of the used precursor. The magnetic behavior of the pre-
pared CFO, Y-CFO, Yb-CFO and Gd-CFO can be understood by the
Neel’s model for ferrimagnetic materials. The Ne el’s magnetic
moment of the prepared samples was calculated by the following
relation45:
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A. Kiran, M.N. Akhtar, M. Yousaf, et al.
Fig. 2. FESEM images of CFO, Y-SFO, Yb-CFO and Gd-CFO spinel ferrite NPs.
Fig. 3. FTIR spectra of CFO, Y-CFO, Yb-CFO and Gd-CFO spinel ferrite NPs.
nB ¼ MB  MA
where, MB and MA are the magnetic moments of the cations at B
and A sites of the prepared NPs which were measured by the cation
distributions over the lattice sites (from XRD data). Furthermore,
initial permeability, anisotropy constant and YeK angles of the REs
Journal of Rare Earths 39 (2021) 1224e1231
doped copper ferrite samples were calculated by the relations as
given below 40:
Hc  Ms
Anistropy constant ¼ (4)
0:96
Ms2  D
mi ¼ (5)
K
 
nB  MA
aYK ¼ cos1 (6)
MB
where, Ms is the saturation magnetizations, Hc is the coercivity and
mi is the initial permeability of the prepared NPs. The calculated
anisotropy constant, YeK angles and initial permeability values are
listed in Table 4. The calculated parameters have different behavior
which corresponds to the substitution of different ionic radii of the
REs elements. The theoretical magnetic moment of the REs doped
elements is Y3þ (3.34 mB ), Yb3þ (4.63 mB ), Gd3þ (7.94 mB ) and Fe3þ (5
mB ) as observed in the literature.46 So, it can be expected that the
magnetization of the prepared NPs should be increased with the
(3) doping of REs elements but in this case the magnetization of the
synthesized samples gradually decreases with the REs substitution.
The similar behavior has been noticed by Zipare et al.47 by the
doping of Dy3þ in MneZn spinel ferrite NPs. They also observed the
decreasing trend in magnetization of MneZn NPs by the substitu-
tion of REs element. The decreasing trend in magnetization by the
1227
A. Kiran, M.N. Akhtar, M. Yousaf, et al. Journal of Rare Earths 39 (2021) 1224e1231

Table 2
XRD internal structural parameter (site radii, bond length, shared edges and unshared edges) of CFO, Y-SFO, Yb-CFO and Gd-CFO spinel ferrite NPs.

Samples Site radii (101 nm) Bond length (101 nm) Shared edges (101 nm) Unshared edges (101 nm)

rA rB RA RB dAE dBE dBEU

CFO 0.7742 0.9343 2.1242 2.2857 3.4688 3.1510 3.3118

Y-CFO 0.7519 0.9104 2.1019 2.2617 3.4325 3.1181 3.2772
Yb-CFO 0.7588 0.9167 2.1078 2.2681 3.4421 3.1268 3.2864
Gd-CFO 0.8057 0.9682 2.1557 2.3196 3.5203 3.1978 3.3610

Table 3
FTIR parameters of CFO, Y-CFO, Yb-CFO and Gd-CFO spinel ferrite NPs.

Composition v2 (cm1) v1 (cm1) kt (  105 Dyne/cm) ko (  105 Dyne/cm)

CFO 644 743 5.1 3.86

Y-CFO 644 720 4.8 3.86
Yb-CFO 645 733 5.01 3.9
Gd-CFO 643 742 5.13 3.85

3.4. Electromagnetic analysis

Fig. 4. MeH loop of synthesized CFO, Y-CFO, Yb-CFO and Gd-CFO spinel ferrite NPs.
substitution of REs elements can be explained by the lattice defects
produced at the lattice sites which further modify the magnetic
interactions of the prepared NPs. The cation distribution of the
synthesized samples directly effects on the magnetic strength of
the ferrites which is because of the magnetic relations between
these parameters. The coercivity values are in the range of 272.60 to
705.60 Oe. It is observed that the coercivity of the prepared NPs
shows different behavior with the doping of REs element which
may be because of magneto crystalline anisotropy. Anwar et al.48
observed the change in coercivity values by the substation of REs
(Dy3þ) from 46.83 to 102.06 Oe. The overall magnetic analysis of the
REs doped Cu ferrite suggests the soft magnetic nature of the NPs
which can be used for magneto dielectric applications.
00
Fig. 5(a,b) show the real part (ε0 ) and imaginary part (ε ) of the
complex permittivity in the 1e6 GHz frequency range for CFO, Y-
CFO, Yb-CFO and Gd-CFO NPs. It is noticed that the permittivity (ε0 ;
00
ε ) shows different behavior with the doping of REs elements, and
REs doped CFO exhibits high permittivity compared to pure CFO
NPs. The real and imaginary parts of the permittivity explain the
electric stored energy (ε0 ) and losses of the materials (ε0 0 ). Gd doped
CFO NPs show the higher ε0 values than other doped elements in
CFO samples. The electromagnetic behavior of all the prepared NPs
strongly depends on the Maxwell Wagner model and Koop’s the-
ory.49 The higher ε0 values of the synthesized samples are observed
at 3 and 4.45 GHz frequency region. The alteration in ε0 values can
be attributed to the grains and grain boundaries effect, which are
operative at high frequency and low frequency regions, respec-
tively. Furthermore, the complex permittivity of the prepared NPs
can be elaborated by the hopping of Fe3þ and Fe2þ ions and cation
distributions.50 The electron hopping between the Fe3þ develops
the dielectric losses with the frequency and the divalent Fe2þ ions
provide strength to interfacial polarization of the prepared spinel
ferrite NPs. Noor et al.51 worked on MneZn doped spinel ferrite
samples and they observed the higher ε0 values at high frequency
region, which is comparable to our work. The imaginary part is
observed and depicted in Fig. 5(b). The values remain constant
except Gd and Yb elements at higher frequency region. The
increasing trends have been noticed in Yb-CFO and Gd-CFO NPs
with the increase in frequency (>2.5 GHz), while pure CFO samples
remain constant and then abruptly increased at 4.1 GHz frequency
region. Actually, the electric dipole generated in the intrinsic REs
doped CFO structure, which leads to the orientation polarization
under the applying external field and may cause to increase in
dielectric losses.
00
Fig. 5 (c,d) show the real and imaginary permeability (m0 ; m ) of
the RE doped CFO samples over the 1e6 GHz frequency range. The
permeability of the materials explains the dispersion relation and

Table 4
Magnetic parameters of synthesized CFO, Y-CFO, Yb-CFO and Gd-CFO spinel ferrite NPs.

Samples Ms (emu/g) Mr (emu/g) Mr/Ms Hc (Oe) Magnetic moment (A,m2) Anisotropy constant (erg/cm3) YeK angles ( ) Initial permeability (H/m)

CFO 51.78 30.28 0.584 705.6 0.57 38058.30 21.75 2.720

Y-CFO 23.08 18.33 0.794 297.2 0.25 7145.18 31.23 2.849
Yb-CFO 32.24 22.16 0.687 537.5 0.35 18051.04 29.32 2.429
Gd-CFO 45.72 28.58 0.625 272.6 0.53 12982.58 25.60 4.843

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A. Kiran, M.N. Akhtar, M. Yousaf, et al.
Fig. 5. The complex real and imaginary permittivity (ε0 ; ε’’) (a, b) and permeability (m0 ; m’’) (c, d) of synthesized CFO, Y-CFO, Yb-CFO and Gd-CFO spinel ferrite NPs.
actual magnetic losses at higher frequency region. Gd-CFO has
higher m0 as compared to other REs doped elements and pure CFO
samples, and increasing trends have been noticed at 2.1 and
3.5 GHz frequency region. The m0 values of the synthesized samples
strongly rely on the applied electric field. While, Gd and Yb doped
CFO NPs exhibit improved magnetic losses at higher frequency
region. The variations in m0 0 were measured and are depicted in
Fig. 5(d). The imaginary permeability or magnetic losses of the
materials can arise due to the domain wall motion.52 Moreover, the
domain wall motion can be affected by the lattice defects which are
created in spinel ferrite structure by the doping of REs metal ions.
The NPs have less magnetic losses at low frequency region, while
increasing trends have been observed with the increase of fre-
quency at higher region. The magnetic losses of pure CFO samples
are noticed at 1.25 GHz frequency, while the RE doped CFO samples
magnetic losses are in the range of 1.30e1.40 GHz. The ionic radii of
the REs elements and metal ions distribution on the lattice sites
may alter the permeability of the materials as is discussed in
literature.50,53 The enhancement in the anisotropy constant by the
doping of REs elements also tuned the spinel ferrite structure
distortion, which may cause to improve the permeability of the
nanoferrites.
Fig. 6. Tangent loss of synthesized CFO, Y-CFO, Yb-CFO and Gd-CFO spinel ferrite NPs.
1229
Journal of Rare Earths 39 (2021) 1224e1231
Fig. 6 shows the tangent losses of the REs doped Cu ferrite at
higher frequency region. The dielectric losses of the materials can
be illustrated by energy dispersion into the dielectric medium and
rely on the Fe3þ and Fe2þ ions. The abrupt changes in the dielectric
loss tangent are observed at 1.94 and 2.78 GHz, and then keep
constant at higher frequency region. The tangent loss at lower
frequency region can be ascribed to dominancy of the grain
boundaries, which require more energy to exchange the electrons
between trivalent and divalent Fe ions. Therefore, at higher fre-
quency region the decreasing trend in grains boundaries may cause
to minimize the dielectric losses of the RE doped spinel ferrite NPs.
However, MaxwelleWagner model also explained the theory of the
emergence of dielectric losses in ferrites.54 The porosity of the
synthesized samples and grain boundaries play key roles in
changing the dielectric losses at higher frequencies. The tangent
loss is inversely proportional to the frequency and the similar trend
has been noticed in dielectric losses by applying the frequency from
1 to 6 GHz.
The ac conductivity (sac ) of the REs doped CFO NPs with the
increase in frequency was analyzed and is depicted in Fig. 7. sac of
the material explains the mixed conduction (ionic þ electronic)
Fig. 7. Ac-conductivity of synthesized CFO, Y-CFO, Yb-CFO and Gd-CFO spinel ferrite
NPs.
A. Kiran, M.N. Akhtar, M. Yousaf, et al. Journal of Rare Earths 39 (2021) 1224e1231

phenomena of the material at higher frequency region. It is noticed

that sac of Yb-CFO and Gd-CFO samples increases with the increase
in frequency, while that of Y-CFO remains constant and that of pure
CFO samples decreases over the higher frequency region. The
conduction mechanism of the spinel ferrite NPs can be governed by
Jonscher’s power law55:

sac ¼ Aun (7)

where, A is the constant (temperature coefficient) and n is the

angular frequency constant. The increase in sac can be justified by
the dominancy of grains at high frequency region (>4 GHz). The REs
doping plays a major role in enhancing the conductivity of the
spinel ferrite NPs by producing lattice defects in the spinel
structure.
00
The variations in the electric modulus (M 0 ; M ) were measured Fig. 9. Quality factor of synthesized CFO, Y-CFO, Yb-CFO and Gd-CFO spinel ferrite NPs.
and are depicted in Fig. 8(a, b). M’ and M ’’ of the REs doped copper
ferrite were analyzed in the 1e6 GHz frequency range. Actually, the
complex electric modulus explains the mobility of the charge car- copper ferrite structure and grain boundaries effect. Fig. 8(b) shows
00
rier in the conduction mechanism.56 It is noticed that M 0 saturated the electric modulus (M ) with the increase in frequency. It is
at low frequency (2.20 GHz) and then finally increased at higher observed that Gd-CFO and Yb-CFO remains constant with the fre-
frequency (3.55e4.23 GHz) region. The complex electric modulus quency, and smaller saturation has been observed at 1.90 and
of the REs doped copper ferrite NPs was calculated by the relations 2.80 GHz region. While, M’’ of pure CFO and Y-CFO shows different
as given below57: behavior with the increase in frequency, and high saturation peak is
noticed at 4.03 GHz in pure CFO sample. The relaxation mechanism
ε0 in spinel ferrite NPs explains the shifting of peaks towards the
M0 ¼ (8) higher frequency region as reported by Pubby et al.55
ðε0 Þ2 þ ðε Þ2
00

Fig. 9 shows the Q-factor of the REs doped copper ferrite sample
with the increase in frequency from 1 to 6 GHz, respectively. The
00
00 ε higher saturation quality factor has been observed at 2.65 GHz
M ¼ (9) frequency. Therefore, the prepared RE doped copper ferrite NPs can
ðε0 Þ2 þ ðε Þ2
00

be used for dielectric applications such as resonant circuit and

The electric modulus (M 0 ) may also depend on the restoring multiple chip inductors. Sharif et al.58 worked on Zr and Mg doped
force deficiency, cations distributions over the lattice sites of the BiFeO3 NPs and they also reported Q-factor values above 2.50 GHz
frequency which is the evidence that the prepared NPs are in good
agreement with the literature.

4. Conclusions

REs doped copper ferrite NPs were successfully prepared by

solegel approach and sintered at 850 ℃ . The single-phase cubic
crystalline structure, agglomerations and grain size effect of the
prepared NPs were confirmed using XRD and FESEM. FTIR explains
the vibrational parameter and phase formation of the synthesized
samples. The saturation magnetization, remanence and coercivity
of the samples verify the soft magnetic nature of RE doped copper
ferrite NPs. VNA was used to analyze the dielectric characteristics in
the higher frequency region (16 GHz). Yb-CFO and Gd-CFO have
the best magnetodielectric nature compared with Y-CFO and pure
CFO NPs. Therefore, the RE (Yb3þ, Gd3þ) doped copper ferrite NPs
can be used for magnetodielectric applications because of their
higher magnetization and less dielectric losses at higher frequency
region.

Acknowledgements

Authors are thankful to the Researcher Supporting Project

number (RSP-2020/61), King Saud University, Riyadh, Saudi Arabia
for the financial support.

References

Fig. 8. (a, b) Electric modulus M’ ðaÞ and M ’’ ðbÞ of synthesized CFO, Y-CFO, Yb-CFO 1. Sarathi P, Prasad G. Structural , magnetic and dielectric study of Cu substituted
and Gd-CFO spinel ferrite NPs. NiZn ferrite nanorod. J Magn Magn Mater. 2016;401:918.

1230
A. Kiran, M.N. Akhtar, M. Yousaf, et al.
2. Naik S, Salker A. Change in the magnetostructural properties of rare earth
doped cobalt ferrites relative to the magnetic anisotropy. J Mater Chem.
2012;22:2740.
3. Zhao LJ, Yang H, Zhao XP, Yu LX, Cui YM, Feng SH. Magnetic properties of
CoFe2O4 ferrite doped with rare earth ion. Mater Lett. 2006;60:1.
4. Ayub M, Gul IH, Nawaz K, Yaqoob K. Effect of rare earth and transition metal
La-Mn substitution on electrical properties of co-precipitated M-type Ba-
ferrites nanoparticles. J Rare Earths. 2019;37:193.
5. Almessiere MA, Slimani Y, Baykal A. Synthesis and characterization of
Co1e2xNixMnxCeyFe2eyO4 nanoparticles. J Rare Earths. 2020;38:188.
6. Sattar A, Wafik A, El-Shokrofy K, El-Tabby M. Magnetic properties of CueZn
ferrites doped with rare earth oxides. Phys Status Solidi. 1999;171:563.
7. Salah L, Moustafa A, Farag IA. Structural characteristics and electrical properties
of copper doped manganese ferrite. Ceram Int. 2012;38:5605.
8. Ashiq MN, Qureshi RB, Malana MA, Ehsan MF. Synthesis, structural, magnetic
and dielectric properties of zirconium copper doped M-type calcium strontium
hexaferrites. J Alloys Compd. 2014;617:437.
9. Shahraki RR, Ebrahimi M, Ebrahimi SS, Masoudpanah S. Structural character-
ization and magnetic properties of superparamagnetic zinc ferrite nano-
particles synthesized by the coprecipitation method. J Magn Magn Mater.
2012;324:3762.
10. Masoudpanah S, Ebrahimi SS, Derakhshani M, Mirkazemi S. Structure and
magnetic properties of La substituted ZnFe2O4 nanoparticles synthesized by
solegel autocombustion method. J Magn Magn Mater. 2014;370:122.
11. Sharma R, Bansal S, Singhal S. Tailoring the photo-Fenton activity of spinel
ferrites (MFe2O4) by incorporating different cations (M¼ Cu, Zn, Ni and Co) in
the structure. RSC Adv. 2015;5:6006.
12. Varshney D, Verma K. Substitutional effect on structural and dielectric prop-
erties of Ni1xAxFe2O4 (A¼ Mg, Zn) mixed spinel ferrites. Mater Chem Phys.
2013;140:412.
13. Kumar A, Sharma P, Varshney D. Structural, vibrational and dielectric study of
Ni doped spinel Co ferrites: Co1xNixFe2O4 (x¼ 0.0, 0.5, 1.0). Ceram Int. 2014;40:
12855.
14. Zaki H, Al-Heniti S, Elmosalami T. Structural, magnetic and dielectric studies of
copper substituted nano-crystalline spinel magnesium zinc ferrite. J Alloys
Compd. 2015;633:104.
15. Balagurov A, Bobrikov I, Maschenko M, Sangaa D, Simkin V. Structural phase
transition in CuFe2O4 spinel. Crystallogr Rep. 2013;58:710.
16. Rais A, Taibi K, Addou A, Zanoun A, Al-Douri Y. Copper substitution effect on
the structural properties of nickel ferrites. Ceram Int. 2014;40:14413.
17. Rahimi-Nasrabadi M, Behpour M, Sobhani-Nasab A, Jeddy MR. Nanocrystalline
Ce-doped copper ferrite: synthesis, characterization, and its photocatalyst
application. J Mater Sci Mater Electron. 2016;27:11691.
18. Qamar S, Akhtar MN, Batoo KM, Raslan EH. Structural and magnetic features of
Ce doped Co-Cu-Zn spinel nanoferrites prepared using sol gel self-ignition
method. Ceram Int. 2020;46(10):14481.
19. Elayakumar K, Sathana V, Kumar RT. Structural and magnetic characterization
of rare earth element cerium-doped nickel ferrite nanoparticles (NiCexFe2xO4)
by sol-gel method with antibacterial activity. J Supercond Nov Magnetism. 2020:
1.
20. Mang CY, Ma ZJ, Luo J, Rao MJ, Zhang X, Peng ZW. Electromagnetic wave ab-
sorption properties of cobalt-zinc ferrite nanoparticles doped with rare earth
elements. J Rare Earths. 2020. https://doi.org/10.1016/j.jre.2020.08.011. In
press.
21. Boda N, Boda G, Naidu KCB, Srinivas M, Batoo KM, Ravinder D, et al. Effect of
rare earth elements on low temperature magnetic properties of Ni and Co-
ferrite nanoparticles. J Magn Magn Mater. 2019;473:228.
22. Almessiere M, Korkmaz AD, Slimani Y, Nawaz M, Ali S, Baykal A. Magneto-
optical properties of rare earth metals substituted Co-Zn spinel nanoferrites.
Ceram Int. 2019;45:3449.
23. Tian C, Yao QR, Tong ZF, Zhou HY, Rao GH, Deng JQ, et al. Effects of Sm-doping
on microstructure, magnetic and microwave absorption properties of BiFeO3.
J Rare Earths. 2021;39:835.
24. Nikzad A, Parvizi R. Presence of neodymium and gadolinium in cobalt ferrite
lattice: structural, magnetic and microwave features for electromagnetic wave
absorbing. J Rare Earths. 2020;38:411.
25. Kanna RR, Sakthipandi K, Kumar AS, Dhineshbabu N, Maraikkayar SSMA,
Afroze AS, et al. Synthesis of dysprosium/MneCu ferrite binary nanocomposite:
analysis of structural, morphological, dielectric, and optomagnetic properties.
Ceram Int. 2020;46(9):13695.
26. Elayakumar K, Manikandan A, Dinesh A, Thanrasu K, Kanmani Raja K, Thilak
Kumar R, et al. Enhanced magnetic property and antibacterial biomedical ac-
tivity of Ce3þ doped CuFe2O4 spinel nanoparticles synthesized by sol-gel
method. J Magn Magn Mater. 2019;478:140.
27. Naresh U, Kumar RJ, Naidu KCB. Optical, magnetic and ferroelectric properties
of Ba0.2Cu0.8xLaxFe2O4 (x ¼ 0.2e0.6) nanoparticles. Ceram Int. 2019;45:7515.
28. Chaudhari D, Shahare A, Nandanwar A, Choudhary D, Rewatkar K. Effect of rare
earth (Gd3þ) cations on structural and magnetic properties of NiZn spinel
ferrites. Studies in Indian Place Names. 2020;40:6130.
29. Mund H, Ahuja B. Structural and magnetic properties of Mg doped cobalt
ferrite nano particles prepared by sol-gel method. Mater Res Bull. 2017;85:228.
1231
Journal of Rare Earths 39 (2021) 1224e1231
30. Kulal SR, Khetre SS, Jagdale PN, Gurame VM, Waghmode DP, Kolekar GB, et al.
Synthesis of Dy doped CoeZn ferrite by solegel auto combustion method and
its characterization. Mater Lett. 2012;84:169.
31. Abdellatif MH, El-Komy G, Azab A, Salerno M. Crystal field distortion of La3þ
ion-doped Mn-Cr ferrite. J Magn Magn Mater. 2018;447:15.
32. Dascalu G, Popescu T, Feder M, Caltun O. Structural, electric and magnetic
properties of CoFe1.8RE0.2O4 (RE¼ Dy, Gd, La) bulk materials. J Magn Magn
Mater. 2013;333:69.
33. Yousaf M, Noor A, Xu S, Akhtar MN, Wang B. Magnetic characteristics and
optical band alignments of rare earth (Smþ3, Ndþ3) doped garnet ferrite
nanoparticles (NPs). Ceram Int. 2020;46(10):16524.
34. Mocherla PS, Karthik C, Ubic R, Ramachandra Rao M, Sudakar C. Tunable
bandgap in BiFeO3 nanoparticles: the role of microstrain and oxygen defects.
Appl Phys Lett. 2013;103, 022910.
35. Akhtar MN, Rahman A, Sulong AB, Khan MA. Structural, spectral, dielectric and
magnetic properties of Ni0.5MgxZn0.5xFe2O4 nanosized ferrites for microwave
absorption and high frequency applications. Ceram Int. 2017;43:4357.
36. Hakim M, Nath SK, Sikder S, Maria KH. Cation distribution and electromagnetic
properties of spinel type NieCd ferrites. J Phys Chem Solid. 2013;74:1316.
37. Zahi S. Synthesis, permeability and microstructure of the optimal nickel-zinc
ferrites by sol-gel route. J Electromagn Anal Appl. 2010;2:56.
38. Yousaf M, Mushtaq N, Zhu B, Wang B, Akhtar MN, Noor A, et al. Electrochemical
properties of Ni0.4Zn0.6Fe2O4 and the heterostructure composites (NieZn
ferrite-SDC) for low temperature solid oxide fuel cell (LT-SOFC). Electrochim
Acta. 2020;331:135349.
39. Yadav RS, Havlica J, Masilko J, Kalina L, Wasserbauer J, Hajdúchova  M, et al.
Impact of Nd3þ in CoFe2O4 spinel ferrite nanoparticles on cation distribution,
structural and magnetic properties. J Magn Magn Mater. 2016;399:109.
40. Akhtar MN, Khan MA. Effect of rare earth doping on the structural and mag-
netic features of nanocrystalline spinel ferrites prepared via sol gel route.
J Magn Magn Mater. 2018;460:268.
41. Rahman S, Nadeem K, Anis-ur-Rehman M, Mumtaz M, Naeem S, Letofsky-
Papst I. Structural and magnetic properties of ZnMg-ferrite nanoparticles
prepared using the co-precipitation method. Ceram Int. 2013;39:5235.
42. Gadkari AB, Shinde TJ, Vasambekar PN. Magnetic properties of rare earth ion
(Sm3þ) added nanocrystalline MgeCd ferrites, prepared by oxalate co-
precipitation method. J Magn Magn Mater. 2010;322:3823.
43. Abdellatif MH, El-Komy GM, Azab AA, Moustafa AM, Salerno M. Crystal field
deformation by Ce3þ doping in spinel Mn-Cr ferrite. J Magn Magn Mater.
2020;502:166517.
44. Abdellatif M, El-Komy G, Azab A. Magnetic characterization of rare earth doped
spinel ferrite. J Magn Magn Mater. 2017;442:445.
45. Nath SK, Maria KH, Noor S, Sikder S, Hoque SM, Hakim M. Magnetic ordering in
NieCd ferrite. J Magn Magn Mater. 2012;324:2116.
46. Yousaf M, Akhtar MN, Wang B, Noor A. Preparations, optical, structural,
conductive and magnetic evaluations of RE’s (Pr, Y, Gd, Ho, Yb) doped spinel
nanoferrites. Ceram Int. 2020;46:4280.
47. Zipare K, Bandgar S, Shahane G. Effect of Dy-substitution on structural and
magnetic properties of MnZn ferrite nanoparticles. J Rare Earths. 2018;36:86.
48. Anwar A, Zulfiqar S, Yousuf MA, Ragab SA, Khan MA, Shakir I, et al. Impact of
rare earth Dy3þ cations on the various parameters of nanocrystalline nickel
spinel ferrite. J Mater Res Technol. 2020;9(3):5313.
49. Maqsood A, Khan K. Structural and microwave absorption properties of Ni(1
x)Co(x)Fe2O4 (0.0 x 0.5) nanoferrites synthesized via co-precipitation route.
J Alloys Compd. 2011;509:3393.
50. Meena R, Bhattachrya S, Chatterjee R. Complex permittivity, permeability and
wide band microwave absorbing property of La3þ substituted U-type hex-
aferrite. J Magn Magn Mater. 2010;322:1923.
51. Noor A, Akhtar MN, Khan S, Nazir MS, Yousaf M. Synthesis, morphological and
electromagnetic evaluations of Ca doped Mn spinel nanoferrites for GHz
regime applications. Ceram Int. 2020;46(9):13961.
52. Stergiou C, Zaspalis V. Analysis of the complex permeability of NiCuZn ferrites
up to 1 GHz with regard to Cu content and sintering temperature. Ceram Int.
2014;40:357.
53. Zhu JW, Guo SB, Chu ZY, Jin WQ. CO2-tolerant oxygen-permeable perovskite-
type membranes with high permeability. J Mater Chem. 2015;3:22564.
54. Wang T, Hu JC, Yang HB, Jin L, Wei XY, Li CC, et al. Dielectric relaxation and
Maxwell-Wagner interface polarization in Nb2O5 doped
0.65BiFeO3e0.35BaTiO3 ceramics. J Appl Phys. 2017;121, 084103.
55. Pubby K, Babu KV, Narang SB. Magnetic, elastic, dielectric, microwave ab-
sorption and optical characterization of cobalt-substituted nickel spinel fer-
rites. Mater Sci Eng, B. 2020;255:114513.
56. Deng LW, Ding L, Zhou KS, Huang SX, Hu ZW, Yang BC. Electromagnetic
properties and microwave absorption of W-type hexagonal ferrites doped with
La3þ. J Magn Magn Mater. 2011;323:1895.
57. Abdel Maksoud MIA, El-Ghandour A, Ashour AH, Atta MM, Abdelhaleem S, El-
Hanbaly AH, et al. La3þ doped LiCo0.25Zn0.25Fe2O4 spinel ferrite nanocrystals:
insights on structural, optical and magnetic properties. J Rare Earths.
2020;39(1):75.
58. Sharif MK, Khan MA, Hussain A, Iqbal F, Shakir I, Murtaza G, et al. Synthesis and
characterization of Zr and Mg doped BiFeO3 nanocrystalline multiferroics via
micro emulsion route. J Alloys Compd. 2016;667:329.