Physica B 650 (2023) 414548

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Physica B: Condensed Matter

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

Dielectric behavior of nanocrystalline Cu-Fe ferrites synthesized by plasma

arc discharge process
N. Mohammadinezhad, Kh. Gheisari *, K. Ranjbar, A. Sabahi
Department of Materials Science and Engineering, Faculty of Engineering, Shahid Chamran University of Ahvaz, Ahvaz, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, nanocrystalline Cu–Fe ferrite powders with the chemical composition of CuxFe1-xFe2O4 (where 0 ≤
CuxFe1-xFe2O4 ferrite x ≤ 0.5) were synthesized via the plasma arc discharge process. Regarding the phase analysis, a spinel structure
Plasma arc discharge of the nanocrystalline Cu–Fe ferrite phase has been developed successfully in all synthesized compositions.
Nanocrystalline
Dielectric properties were measured in the 100 Hz to 10 MHz range using an LCR meter. Results show that the
Dielectric constant
AC conductivity
substitution of Cu for Fe ions leads to a substantial increase in the dielectric constant due to the migration of
some Fe3+ ions from tetrahedral to octahedral sites and the formation of Cu+/Cu2+ ion pairs in the octahedral
sites contributing to the hopping process. The results also indicate that the low-frequency dielectric constant is
influenced by grain boundary capacitance while grain capacitance plays a major contribution to the dielectric
constant in the high-frequency region.

1. Introduction findings, a magnetic saturation of 88.3 emu/g has been observed which
is superior to that reported for Cu ferrite prepared by most other
Although soft magnetic ferrites are well-known due to their methods such as ball milling (51.1 emu/g) [18], exploding wire (28
outstanding electromagnetic properties such as low magnetic loss and emu/g) [19], solvothermal (53.1 emu/g) [20], sol-gel (42.2 emu/g)
high magnetic permeability in the high-frequency region, they have also [21], solid-state reaction (22.1 emu/g) [22], co-precipitation 29.4–30.8
attracted interest because of their high dielectric constant; therefore, emu/g [23,24], hydrothermal [25], microwave-hydrothermal (56.2
soft magnetic ferrites are sometimes termed multiferroics [1–3]. The emu/g) [26], microwave combustion (66.4 emu/g) [21], citrate-nitrate
combined effects of magnetic and dielectric properties allow them to be combustion (20.6 emu/g) [27], thermal decomposition (29.1 emu/g)
used as suitable candidates in magneto-electronics devices such as iso­ [22], sonochemical (0.086 emu/g) [28], and nano casting (22 emu/g)
lators, switches, cores for high-frequency transformers, etc. [4,5]. The [29].
characteristics of the spinel ferrites are strongly dependent on several The PAD process is a simple, flexible, fast, and cost-effective powder
parameters, the most important of which are chemical composition, synthesis method developed based on high-temperature arc plasma
preparation method, cation distribution, and grain size [6,7]. established by passing a high current through the electrodes (initial
Cu ferrite is one of the most important soft magnetic ferrites which is materials) followed by a high cooling rate [30–34]. A wide range of
well-known due to its high Curie temperature (≈500 ◦ C) [8], high ultra-fine solid particle materials with narrow particle size distribution
electrical resistivity (≈105 Ω cm) [9], low cost, and it is environmentally including metallic, ceramic, carbides, borides, and nitrides can be pro­
benign [10,11]. Moreover, Cu ferrite has a band gap of approximately duced by this process [33,35,36].
1.32 eV making it effective under visible light irradiation [12]. The The dielectric behavior of the spinel ferrites originates from charge
outstanding properties of Cu ferrites make them suitable for a wide carriers hopping between cations with different valence states distrib­
range of potential applications such as photocatalysts [12], electro­ uted randomly on the neighboring octahedral lattice sites. Additionally,
catalysts [13], electrochemical sensors [14], humidity sensors [15], low-resistivity grains and high-resistivity boundaries make a significant
anode material for Li-ion batteries [16], etc. contribution to the dielectric permittivity [37]. The studies on dielectric
In our previous work [17], nanocrystalline Cu ferrite powders were properties are not only important from an application point of view but
synthesized via the plasma arc discharge (PAD) process. Based on our they also provide some additional information on the structural aspects

* Corresponding author.
E-mail address: [email protected] (Kh. Gheisari).

https://doi.org/10.1016/j.physb.2022.414548
Received 9 October 2022; Received in revised form 24 November 2022; Accepted 28 November 2022
Available online 2 December 2022
0921-4526/© 2022 Elsevier B.V. All rights reserved.
N. Mohammadinezhad et al. Physica B: Condensed Matter 650 (2023) 414548

of dielectric materials. Therefore, they help in having a fundamental

perspective and comprehensive idea of the insulation characteristics. On
the other hand, it has been found that the dielectric properties of the
spinel ferrites are significantly influenced by the synthesis methods [37]
in such a way that different values of dielectric constant have been re­
ported for similar compositions synthesized by different techniques [2].
Although in recent years, numerous investigations on the dielectric
properties of various types of spinel ferrite composites have been re­
ported in the literature, the electrical properties of the Cu–Fe ferrite
have not been considered extensively. Furthermore, to the best of our
knowledge, no detailed report has been sighted in the literature on the
electrical properties of Cu2+ doped FeFe2O4 ferrite nanoparticles syn­
thesized using PAD process. This paper follows our previous research
[17], in which the structure, microstructure, and magnetic properties of
CuxFe1-xFe2O4 (x = 0, 0.3, 0.5, 0.7, and 1) powder particles synthesized
using the PAD process have been investigated in detail. Following the
outstanding results obtained in the previous work, in the present work,
an attempt has been made to study the influence of Cu ions substitution
on the dielectric, impedance, and electrical transport characteristics of
Fe–Cu ferrites synthesized using the PAD process.

2. Experimental methods

Nanocrystalline spinel ferrite powders with the chemical formula

Cu2+ 2+ 3+ 2−
x Fe1− x Fe2 O4 (x = 0, 0.3, 0.5, 0.7, and 1) were prepared by the
Fig. 1. XRD patterns of the as-synthesized CuxFe1-xFe2O4 powders.
PAD process in a vertical chamber using an electrical current of 200 A in
the air atmosphere. High-purity of iron and copper powders (purity
>99%) were mixed according to the stoichiometric ratio of each is defined to reflect this increase in the capacitance or the ability to store
composition. The initial average particle size of the Fe and Cu powders electric charge by having a dielectric medium [38]. The dielectric con­
were in the range of 37 ± 5.7 μm and 5.58 ± 0.44 μm, respectively. The stant of the medium can be calculated using the measured capacitance
mixed powders were cold compacted into cylindrical bars of about 10 value C from the following relation [39]:
mm diameter and 20 mm height at a pressure of 900 MPa, then were Ct
(1)
′
used as anode and cathode in the chamber of the arc plasma reactor. ε =
ε0 A
Further information regarding the experiment has been described else­
where [17,30]. The X-ray diffraction (XRD) patterns were obtained In this expression, the symbols εₒ, A, and t represent the permittivity
using Philips diffractometer PW-1840 with Cukα1 radiation. For of free space (8.85 × 10− 12 F/m), the cross-section area of the pellet, and
dielectric and impedance spectroscopy measurements, the as-prepared the thickness of the pellet, respectively.
powders were mixed with 4 wt% phenolic resin, uniaxially pressed The frequency dependence of ε′ displayed in Fig. 2 exhibits the
into circular disc-shaped pellets (d = 10 mm and t = 2 mm) at a pressure typical response of Cu ferrites to the applied AC electric field which has
of 130 MPa, and then cured in 150 ± 10 ◦ C for 45 min. Due to the similar been observed earlier [19,39–41]. Dielectric constant demonstrates
powder processing applied to all samples, the density is obtained in a maximum values at low frequency, then drops rapidly due to increasing
similar range with narrow distribution (48 ± 3%). The smooth and
parallel surfaces of the pellet were coated with high-purity silver paste.
The coated pellet surfaces make parallel-plate capacitors with ferrite
material as the dielectric medium in the region between the plates. The
dielectric properties were measured at room temperature using a 20
Hz-10 MHz Digital LCR Meter (GWINSTEC, LCR-8110G) by applying AC
potential signal across the parallel plate capacitors.

3. Results and discussion

3.1. Structure

Fig. 1 shows the X-ray diffraction patterns of the as-synthesized

Cu–Fe ferrite powders. Regarding the obtained diffraction patterns,
the spinel structure of soft magnetic ferrite with Fd3m space group
symmetry has been formed successfully in all samples. Based on the
broadening and the angular position of diffraction lines, the estimated
values of crystallite size and lattice parameter are in the range of 39–59
nm and 8.3812–8.3512 nm, respectively. More details can be found in
Ref. [17].

3.2. Dielectric constant Fig. 2. Variation of the real part of dielectric constant as a function of fre­
quency for CuxFe1-xFe2O4 ferrite. The solid lines are fitted to the experimental
The real component of the permittivity, or the dielectric constant, ε′ points (open symbols) based on the modified Debye’s function.

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N. Mohammadinezhad et al. Physica B: Condensed Matter 650 (2023) 414548

frequency and ultimately becomes roughly frequency independent at all spinel ferrite samples doped with different concentrations of copper
high frequencies. ions in this work [17], the compositional variation of ε′ may be due to
In general, the dielectric constant of the insulators originated from the strong correlation between dielectric properties and cation distri­
four types of polarization mechanisms, namely electronic, orientational bution on the B-sites. The cation distribution of the Cu–Fe ferrite system
(dipolar), ionic, and interfacial (space charge) polarization [42]. How­ synthesized via the PAD process was estimated based on the observed
ever, orientational, ionic, and electronic polarization will be able to keep value of the net magnetic moment reported in Ref. [17]. The cation
up with the changing field up to the frequency of ≈ 109, 1013 Hz, and ≈ distribution on the octahedral sites is also presented in Fig. 3. Accord­
1015 Hz, respectively. Hence, the variation of ε’ with frequency at the ingly, the introduction of Cu ions into the spinel structure results in an
frequency range measured in this study (<107 Hz) just can be explained increase in the number of Fe3+ ions and Cu2+ ions at the B-sites while the
based on the interfacial polarization [2,42]. number of Fe2+ ions at the B-sites decreases due to the substitution of the
The interfacial polarization can be described based on the micro­ Cu dopants. The upward trend of the ε′ with Cu2+ ion concentration may
structure of polycrystalline ferrites composed of highly conducting be attributed to the migration of some Fe3+ ions from A-sites to B-sites
grains surrounded by relatively poorly conducting grain boundaries. enhancing the electron exchange between Fe2+/Fe3+ ion pairs.
When an external AC electric field is applied, the electron hopping Furthermore, due to the unstable valency of Cu cations, electron transfer
(exchange) is started between ions of different valence states on the can occur between Cu+/Cu2+ ion pairs or between Fe and Cu cations.
tetrahedral (A) and octahedral (B) sites such as Fe3+ and Fe2+ pairs of In the Cu2+ 2+ 3+ 2−
x Fe1− x Fe2 O4 ferrite system, more than one ion (O ,
2−

ions. However, since the available Fe2+ ions prefer to occupy B-sites, 2+ 2+ 3+
Cu , Fe , and Fe ) contributes to the dielectric relaxation process.
Fe2+/Fe3+ interactions may make a major contribution to the polari­ Under these conditions, the dielectric relaxation behavior can be
zation in the spinel ferrite [43]. In addition, the lowest distance between described using modified Debye’s relaxation function. Accordingly, the
√̅̅̅
two cations on B-sites ((a /4) 2) is smaller than that between two cat­ dispersion of the dielectric constant can be modeled as [37,47]:
√̅̅̅ √̅̅̅̅̅̅
ions on A-sites ((a /4) 3) and A-B sites ((a /8) 11) [9]. Therefore, the ( ′ ′ )
ε0 − ε∞
probability of hopping between A–A sites and A-B sites is much lower (2)
′ ′
ε = ε∞ +
compared to that occurring between adjacent B-sites [44]. 1 + (ωτ)2(1− α)
In the low-frequency region, charge carriers released through the
where ε∞ is the dielectric constant at a higher frequency (at 5 MHz), ε0 is
′ ′

electron hopping mechanism can pass over the grains and reach the
grain boundaries or interphase interfaces. Due to the high resistivity of the dielectric at the lowest frequency (here at 100 Hz), ω is the angular
the grain boundaries, charge carriers are accumulated to build up charge frequency, τ is the mean relaxation time, and α is the spreading factor of
layers at the internal interfaces, leading to a great contribution to the the actual relaxation times about the mean value.
dielectric constant. Nevertheless, as the frequency of the applied field Curve fitting of experimental data (open symbols) using the modified
increases, the direction of the applied field, and therefore, the direction Debye’s relaxation function (solid lines) is shown in Fig. 2 and the ob­
of the charge carrier’s motion is reversed before they can pile up at the tained parameters including the mean relaxation time and the spreading
grain boundaries. Hence, the interfacial polarization and dielectric factor are presented in Table 1. The model fitting shows that the
constant decrease as a result of the decrease in the probability of the experimental data is in good agreement with the calculated data, con­
charge carriers reaching the internal interfaces [2,45]. firming that more than one ion contributes to the relaxation process [48,
It is worth noting that the dielectric constant of nanoferrites is 49]. Hence, the modified Debye model is appropriate to describe the
significantly influenced by structural and microstructural parameters dispersion in the dielectric constant and the dielectric relaxation process
such as stoichiometric composition, particle size, cation distribution, in the present study.
and oxygen vacancies [46]. The maximum value of the dielectric con­ As shown in Table 1, there is a strong correlation between the
dielectric constant at low frequency and the relaxation time. The ε0 and
′
stant measured at the lowest measured frequency (i.e., 100 Hz in which
the contribution of the interfacial polarization is predominated) is τ are much higher for CuFe2O4 compared to pure Fe3O4. It has been
shown in Fig. 3 as a function of Cu content. The value of the dielectric shown that there is a direct relationship between the relaxation time and
constant is found to increase with an increase in Cu2+ ion concentration. O–Me bond length in the octahedral site [47]. This increase in bond
Regarding the similar crystallite and particles size values observed for lengths leads to an increase in the atomic polarizability, which in turn
causes an increase in the dielectric constant [49]. The mean value of
O–Me bond length in the B sites was estimated according to the cation
distribution on the B-sites presented in Fig. 3. The obtained data
(Table 1) exhibits that the highest O–Me bond length as well as the
highest τ and ε0 is observed in the CuFe2O4.
′

A recent review of the literature on this topic shows that the obtained
value of the dielectric constant at 100 Hz for the CuFe2O4 ferrite syn­
thesized in the study (i.e., 5755) is much higher than the earlier reported
values of the nano CuFe2O4 ferrite prepared by explosion technique
(≈20) [19] and sol-gel auto-combustion technique (≈700) [39]. This
comparison confirms the superior dielectric properties of the Cu–Fe

Table 1
Bond length between cation-anion on octahedral site (Me–O) and dielectric
parameters including the relaxation time (τ) and spreading factor (α) obtained
by fitting the experimental data to the modified Debye’s relaxation function.
x Me–O (Å) τ (s) α ε0 (at 100 Hz)
′
ε∞ (at 5 MHz)
′

− 4
0 1.980 2.4 × 10 0.71 1245 53
4
0.3 1.984 4.9 × 10− 0.77 1200 67
4
0.5 1.987 7.6 × 10− 0.62 3280 57
4
0.7 2.000 6.1 × 10− 0.66 1686 59
Fig. 3. The dielectric constant measured at 100 Hz and cation distribution on 4
1 2.008 9.4 × 10− 0.61 5755 50
the octahedral sites for various Cu2+concentration in the CuxFe1-xFe2O4 series.

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N. Mohammadinezhad et al. Physica B: Condensed Matter 650 (2023) 414548

ferrite system synthesized via the PAD process which may be ascribed to kHz (i.e., logω = 4.50) where conductivity is a frequency-independent
the desirable cation distribution obtained in the PAD method, leading to term, and one above 200 kHz (i.e., logω = 6.10) where conductivity is
an appropriate combination of the magnetic and dielectric properties. heavily frequency dependent and logσ increases linearly with logω.
Generally, the total bulk conductivity of ferrites complies with
3.3. Dielectric loss Jonscher’s power law as follows [37]:
σ t = σ DC (T) + Aωn (4)
The energy loss of the dielectric materials can be reported in terms of
the imaginary component of the dielectric constant (ε’’) [42]. The where σDC(T) is DC conductivity, A is the temperature-dependent
dielectric loss in the polycrystalline ferrites is caused by the energy parameter that determines the strength of the polarizability and n is
dissipation in the form of heat due to resistance of the internal friction the power law exponent that lies between 0 and 1 specifying the
against the hopping conduction of charge carriers [50]. The frequency increasing rate of AC conductivity with frequency. The first term, which
dependence of ε’’ for various compositions is presented in Fig. 4. The is frequency-independent conductivity, designates DC conductivity
variation of ε’’ with frequency is similar to that observed for ε’ with owing to band conduction. DC conductivity increases with increasing
frequency, i.e., it initially decreases with increasing frequency and temperature due to thermal energy promoting transition electrons from
finally becomes nearly constant in the high-frequency region. This type the valence band to the conduction band [37]. In contrast, the second
of dispersion can be explained based on the interfacial polarization that term, which is both temperature and frequency-dependent, determines
occurred at the grain boundaries of the heterogeneous microstructure of AC conductivity caused by the hopping processes [45].
the polycrystalline ferrites. In the low-frequency region, due to the On the other hand, in the low-frequency region where conductivity
charge carriers accumulated at the high resistive boundaries, the hoping shows a frequency-independent characteristic, high resistive grain
process requires relatively high energy; consequently, a high value of boundaries are more active. On the contrary, in the high-frequency re­
energy is dissipated. On the contrary, with increasing frequency, the gion where logσ increases directly with logω, conducting grains play a
grain interior with lower resistivity has a major contribution to the dominant role in the conduction mechanisms. In this region, the increase
polarization; hence, little energy is needed for the hopping process, in frequency improves the rate of hopping between the charge carriers,
reducing the energy dissipation [45,50]. and therefore, the AC conductivity rises [44].
Similar to the ε’, the variation of ε’’ with Cu content follows an The value of σDC, A, and n can be determined by fitting the experi­
upward trend. The highest Cu2+ concentration is the highest value of the mental data to Jonscher’s power law, as shown in Fig. 5a. The fitting to
imaginary component of the permittivity at all measured frequencies. the model shows that the experimental data are in good agreement with
The increase of energy loss with Cu2+ concentration may be associated the theoretical calculation results. Variation of the exponent n and DC
with the increase of the total number of charge hopping due to the conductivity as a function of Cu concentration is shown in Fig. 5b. The
migration of Fe3+ ions from A-sites to B-sites in the Cu-enriched spinel exponent n specifies the increasing rate of AC conductivity with fre­
structure or may indicate that the charge transfers between Cu+/Cu2+ quency. Note that fluctuations of the exponent n with Cu content are
ion pairs need more energy. opposite to that observed for DC conductivity. The highest σDC is ob­
tained for CuFe2O4 composition while the lowest exponent parameter n
3.4. Electrical conductivity is observed in this composition. Similar behavior was also reported for
Zn-doped Li ferrites [2].
The frequency dependence of conductivity may be computed from The composition dependence of the increasing rate of σAC with fre­
the relationship [41]: quency may be explained following the pumping force of the applied
field. It is believed that the presence of Cu+/Cu2+ ion pairs in the B-sites
(3)
′
σ = ε0 ε ω tan δ leads to the formation of p-type charge carriers (p-type semiconductor),
while Fe2+/Fe3+ ion pairs occupied in B-sites form n-type charge carriers
where ω is the angular frequency and tanδ is the loss tangent.
(n-type semiconductor) [44]. Increasing the frequency of the applied
The conductivity was calculated and plotted versus the frequency on
field may improve the electron exchange between Fe3+ and Fe2+ ion
a log-log scale in Fig. 5a. Two distinct regions are observed, one below 5
pairs more effectively than the hole hopping between Cu+ and Cu2+
(p-type semiconductor).

3.5. Complex impedance analysis

Impedance spectroscopy is a powerful diagnostic tool for studying

the electrical behavior of electroceramics material, including the charge
carrier behavior as a function of frequency. The frequency dependence
of the real (Z′ ) part of the complex impedance is shown in Fig. 6a. In the
low-frequency region, Z′ shows a frequency-independent characteristic.
The substitution of copper up to x = 1 in CuxFe1-xFe2O4 decreases the
impedance value in this region, probably due to the reduction in the
band gap. However, as depicted in Fig. 6a, Z′ starts to decrease sharply
with a further increase in frequency, indicating that the conduction
mechanism has been dominant because of the charge carrier hopping
[39].
The variation of the imaginary part (Z′′ ) of the complex impedance
with frequency is displayed in Fig. 6b. Z′′ first increases with the increase
of frequency to a maximum value at a particular frequency and then
starts to decrease gradually with a further increase of frequency. The
appearance of a peak in the imaginary part of complex impedance in­
Fig. 4. Frequency-dependent imaginary component of dielectric constant for dicates the presence of space–charge relaxation and the peak point
CuxFe1-xFe2O4 series. shows the relaxation frequency [44]. The shifting of the relaxation

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N. Mohammadinezhad et al. Physica B: Condensed Matter 650 (2023) 414548

Fig. 5. (a) Variation of logσ with logω. The solid lines are fitted to the experimental data (open symbols) according to Jonscher’s power law for all the samples. (b)
The dependence of σDC and exponent parameter n on Cu2+concentration in the CuxFe1-xFe2O4 series.

Fig. 6. The frequency dependence of the (a) Zʹ and (b) Zʺ for CuxFe1-xFe2O4 ferrite samples.

frequency to a higher frequency is attributed to the increase in the

sample conductivity [37], as can be confirmed by Fig. 5a.
The dielectric relaxation phenomenon occurs when the natural fre­
quency of charge carriers hopping coincides with the frequency of the
applied field [51]. The frequency-dependence of real and imaginary
parts of the complex impedance as well as AC conductivity and dielectric
constant are shown for CuFe2O4 ferrite in Fig. 7. At the frequencies
lower than the relaxation frequency, where high resistive grain bound­
aries play a major role, the charge carriers can pass over the conductive
grains and reach the resistive grain boundaries, leading to the higher
values of dielectric constant and lower values of AC conductivity. In
contrast, at frequencies higher than the relaxation frequency, where the
conductive grain boundaries are more effective, the direction of the
charge carrier’s motion is reversed before they can pile up at the insu­
lating grain boundaries. Therefore, the dielectric constant decreases and
becomes nearly constant while AC conductivity sharply increases owing
to the electron hopping process that occurs within the conductive grains.
More details about the conduction mechanism can be understood
from the complex impedance spectrum. In a complex impedance spec­
trum, known as Nyquist plot or Cole-Cole plot, the imaginary part of
complex impedance (Z′′ ) is plotted against the real part of complex Fig. 7. The frequency variation of ε′ , Z′ , Z′′ and σAC for CuFe2O4 ferrite.
impedance (Z′ ), as shown in Fig. 8. The impedance spectrum can be

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N. Mohammadinezhad et al. Physica B: Condensed Matter 650 (2023) 414548

bi-layered microstructure in which conducting grains become aligned

parallel to the resistive grain boundaries and the electrode surface, a
condition that is represented schematically in Fig. 9 [44,52].
Conductive grains and resistive grain boundaries may be distin­
guished from each other in the complex-plane impedance diagram by
two-time constants, τg = RgCg and τgb = RgbCgb. Accordingly, two
semicircles may appear on the Nyquist diagrams. The low-frequency
semicircle corresponds to relaxations in the low-conductivity contin­
uous phase and the high-frequency semicircle to relaxations in the
conductive phase. However, these semicircles are well resolved in the
impedance spectrum if their corresponding time constants are different
as a result of differences in capacitance [52]. Fig. 8 shows that just one
semicircle is observed in the impedance spectra of the Cu–Fe ferrite
systems synthesized in the present study, indicating that characteristic
time constants are not well separated, probably due to their similar
capacitance values. Table 2 lists the equivalent circuit parameters
extracted from Nyquist plots by fitting the curves with the two-RC Voigt
model shown in Fig. 9. The fitting of the models to the experimental data
was performed based on the non-linear least squares fitting method
using Z-view impedance analyzer software. It is found that there is a
close relationship between σDC and Cgb. Since in the low-frequency re­
gion the charge carrier accumulated at the boundaries, the grain
Fig. 8. Graphical representation of imaginary versus real parts of impedance boundary capacitance plays an important role in determining the con­
(Nyquist plots) for CuxFe1-xFe2O4 ferrite powders. duction mechanisms. In addition, the build-up of charge layers at the
boundaries in the low frequencies results in the high value of the
interpreted based on the brick layer model in which conducting grains dielectric constant. The higher the value of the grain boundary capaci­
(discontinuous phase) are separated by resistive grain boundaries tance, the higher the value of the dielectric constant. As shown in
(continuous phase). If conduction along the grain boundaries is negli­ Table 2, CuFe2O4 ferrite exhibits the highest value of ε′ at 100 Hz (5755)
gible and grains themselves are highly conductive, the impedance data owing to the highest value of Cgb (174.70 pF). In contrast, at the high
can be modeled by an equivalent electrical circuit called the two-RC frequencies where conducting grains become more active, the dielectric
Voigt structure. constant exhibits a high dependence on Cg. CuFe2O4 ferrite that has a
This simple Voigt structure which is shown in Fig. 9 consists of two minimum Cg of 23.54 pF also has a minimum ε′ of 52 at 10 MHz.
parallel RC equivalent circuits in a series configuration as (RgCg) Likewise, Cu0⋅3Fe2⋅7O4 ferrite that has a maximum Cg of 43.58 pF also
(RgbCgb), where Rg and Cg are the resistance and capacitance of grains has a maximum ε′ of 77 at 10 MHz.
and Rgb and Cgb are the resistance and capacitance of grain boundaries.
Elements of this equivalent circuit describe the impedance behavior of a 3.6. Complex electrical modulus analysis

The electrical properties of dielectric materials can also be presented

in terms of complex electric modulus M* = M’ + jM′′ , where M′ and M′′
are the real and imaginary parts of the electric modulus, respectively.
The complex electric modulus is related to the complex impedance by
the following relation [50]:

(5)
′ ′
M∗ = M + jM′′ = − ωC0 Z′′ +jωC0 Z

where ω is the angular frequency and C0 is the geometric capacitance.

The frequency dependence of M′ and M′′ is displayed in Fig. 10. It is
evident from Fig. 10a that the values of the real component of the
electric modulus approach a very low value in the low-frequency range.
After that, M′ increases continuously with the increase of frequency and
finally tends to saturate. This behavior may have resulted from the short-
range mobility of charge carriers [53].
The variation of Mʹʹ with frequency shows a strong peak and the
frequency of the peak point is highest for the CuFe2O4 composition
(Fig. 10b). At frequencies lower than the peak position, the charge
carriers can move over long distances. While at frequencies higher than
peak position, charge carriers are mobile on short distances. However, a
high degree of peak broadening indicates that the transition frequency
range from long-range to short-range mobility is wide [54]. In addition,
the asymmetric plot of M′′ may be due to the stretched exponential
character of the relaxation times [37].
The stretched exponent parameter (β) can be estimated by fitting
imaginary modulus spectra to the modified KWW (Kohlrausch-Williams-
Watts) function [55]:
Fig. 9. (a) Brick layer model representing a system consisting of conductive
grains separated by resistive grain boundaries. (b) Voigt structure consists of
two RC circuits.

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N. Mohammadinezhad et al. Physica B: Condensed Matter 650 (2023) 414548

Table 2
The equivalent circuit parameters extracted from Nyquist plots by analyzing the complex impedance data using Z-view impedance analyzer software.
x Rgb (kΩ) Cgb (pF) τgb (μs) Rg (kΩ) Cg (pF) τg (μs) σDC × 103 (S m− 1) ε′ at 100 Hz ε′ at 10 MHz
0 91.31 62.61 0.57 7.75 30.65 0.24 0.22 1245 56
0.3 26.10 90.47 2.36 7.75 43.58 0.34 0.73 1200 77
0.5 34.56 84.74 2.93 12.59 31.15 0.39 0.51 3280 61
0.7 101.59 67.36 6.84 18.00 35.97 0.65 0.21 1686 62
1 6.81 174.70 1.19 6.70 23.54 0.16 1.78 5755 52

Fig. 10. The frequency dependence of the (a) Mʹ and (b) Mʺ for CuxFe1-xFe2O4 ferrite samples.

M′′
M′′ = [ max
( ) ( )β ] (6)
β
(1 − β) + 1+β β f max
f
f
+ f max

where M′′max is the peak maxima and fmax is the corresponding frequency.
β value normally lies between 0 and 1 and determines whether the
dielectric relaxation is Debye or non-Debye in nature. For an ideal
dielectric, the stretched coefficient is equal to unity, indicating Debye-
type relaxation where dipole-dipole interaction is negligible. Never­
theless, when the stretched coefficient is less than unity, the dipole-
dipole interaction is considerable, representing non-Debye type relaxa­
tion. Fig. 11 displays the typical fitting of the modified KWW function to
the experimental M′′ data obtained for CuFe2O4 ferrite. The fitting to the
modified KWW function exhibits that the measurement data are in good
agreement with the calculated data. The stretched coefficient and the
peak frequency of M′′ are extracted from curve-fitting and also are
shown as a function of Cu2+ concentration in Fig. 11. The obtained
values of β are in the range of 0.17–0.47, indicating that the relaxation
present in the CuxFe1-xFe2O4 ferrites is non-Debye type.
Debye or non-Debye nature of the dielectric relaxation can also be
confirmed using simultaneous evaluation of the frequency-dependent
behavior of Mʹʹ and Zʹʹ. In addition, it can help us understand whether
the relaxation process is dominated by long-range or short-range Fig. 11. Fitting of M′′ spectrum to modified KWW equation for CuFe2O4 ferrite
movement of charge carriers. When the peak frequency of Z′′ and M′′ as well as the variation of stretched parameter (β) and the frequency of the peak
spectra is similar, the relaxation process is dominated by the long-range maximum (fmax) with Cu2+ concentration extracted from curve-fitting. The
movement of charge carriers (Debye-type relaxation). Nevertheless, continuous line represents the fitted value of M′′ whereas the open symbol
when there is a wide gap between the peak frequency of Mʹʹ and Zʹʹ represents the experimental data.
spectra, the relaxation process is dominated by the short-range move­
ment of charge carriers (non-Debye type relaxation) [37]. The consid­ dominant role in the dielectric relaxation, confirming non Debye type of
erable gap between the peak positions of the Z′′ and M′′ plots versus behavior.
frequency can be observed for all ferrite systems studied in the present
work. The typical spectra of Z′′ and M′′ for CuFe2O4 are presented in 4. Conclusions
Fig. 12. The non-coincidence of the peak frequency of Z′′ and M′′ in­
dicates that the short range movement of charge carriers plays a In this study, nanocrystalline CuxFe1-xFe2O4 (where 0 ≤ x ≤ 0.5)

7
N. Mohammadinezhad et al. Physica B: Condensed Matter 650 (2023) 414548

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