Journal of Alloys and Compounds 879 (2021) 160432

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Journal of Alloys and Compounds

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Fabrication of different rare earth incorporated ZnCo2O4 matrix via

chemical-mechanical hybrid mechanism and study their charge carrier ]]
]]]]]]
]]

dynamics by Motts VRH model

⁎
Bithika Mandal, Rajdip Roy, Partha Mitra
Department of Physics, The University of Burdwan, Burdwan 713104, India

a r t i cl e i nfo a bstr ac t

Article history: This work reports how microstructural and electrical property varies with different rare-earth (Nd, Sm, Gd,
Received 19 January 2021 Dy and Y) incorporation in spinel structured ZnCo2O4 nano-cobaltite. These materials have been synthe­
Received in revised form 29 April 2021 sized using a combination of both chemical and physical methods. Host spinel material was prepared
Accepted 13 May 2021
through chemical co-precipitation method and mechanical milling was used to reinforce the rare earth
Available online 21 May 2021
oxides into the spinel structure. Structural, microstructural, elemental and optical characterization has been
carried out using XRD, FTIR, FESEM, EDX and UV-Vis spectroscopy. XRD confirms the formation of the
Keywords:
Ball milling nanocrystalline materials. Different microstructural parameters like lattice parameters, microstrain, crys­
Rare earth tallite size and x-ray density have been estimated from Rietveld analysis, which shows particle size of the
Rietveld refinement doped samples depends on size of the dopant rare earth. Positions of different bonds have been confirmed
Hybrid mechanism from FT-IR analysis. FESEM micrographs confirm particle dimensions of the agglomerated spherical grains
Mott theory are in good agreement with Rietveld output. Optical band gap increases with decreasing dopant radii from
3.48 eV to 3.99 eV. Impedance plots show highest conductivity achieved was 1.151 × 10−3 Ω−1cm−1 at 433 K
for Yttrium doped ZnCo2O4 nano-composition with lowest activation energy of 0.34 eV. Temperature de­
pendent frequency exponent explains small polaron hopping transaction. Impedance master curves obey
time-temperature superposition principle. Motts VRH model applied to electrical properties to get an
insight about electrical conduction mechanism of the prepared samples.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction like co-precipitation, combustion, sol-gel, sputtering, auto-ignition,

electrodeposition, solvothermal, hydrothermal etc. [11–15]. But
Nanosized metal oxide complexes have attracted many re­ among all these preparation techniques, co-precipitation method is
searchers in recent years for their widespread and praiseworthy easy, low-cost and worthy for its control on particle size and other
application prospects in different fields. These semiconducting na­ synthesis conditions. There are many synthesis conditions like ex­
nocompounds possess unique properties due to their high surface to perimental temperature, stirring rate, pH of the reaction mixture,
volume ratio, quantum confinement effect, better reaction rate, in­ concentration of precursors etc. Each condition can be controlled in
traparticle interaction etc. [1,2]. Among different nanostructured co-precipitation method [16]. Among many binary metal oxide spi­
materials, mixed oxide spinels exhibit interesting and widespread nels like NiCo2O4, CuCo2O4, MnCo2O4, FeCo2O4, Zinc cobaltite with
application in various electrical, electrochemical, optoelectronic and normal spinel structure seeks many researchers attention due to its
magnetoelectronic devices [3–5]. Spinels have attracted researchers tuneable structure features, chemical, electrical, magnetic and
for their enormous applications in electronic and optoelectronic electrochemical properties. ZnCo2O4 material is found to have
devices like solid oxide fuel cells (SOFCs), energy conversion devices, superior oxygen ion conductivity, so it can be used as electrolyte
lithium-ion batteries, supercapacitors, gas sensors, oxygen sensors, material in SOFC and the applicability is tuned by appropriate
photovoltaic system etc. [6–10]. These heterometallic spinel oxides amount of doping with different ions (cations) into the spinel
can be fabricated through various chemical and mechanical methods structure [17]. Zinc cobaltite has normal spinel structure with di­
valent Zinc ions in tetrahedral voids and trivalent Cobalt ions in
octahedral void. Due to this co-existence of two types of cations and
⁎
Corresponding author. dopant cation, multiple oxidation states has been created which
E-mail address: [email protected] (P. Mitra).

https://doi.org/10.1016/j.jallcom.2021.160432
0925-8388/© 2021 Elsevier B.V. All rights reserved.
B. Mandal, R. Roy and P. Mitra Journal of Alloys and Compounds 879 (2021) 160432

intern helps to conduct the charges. Significantly high electrical (28–30%) was added dropwise to the solution until it attains a
conductivity satisfies its appropriate quality as an interconnect pH value ~ 8. Finally, the stirrer was turned off and the solution was
material in SOFC. Physical and chemical properties of doped spinel kept at 80 °C for 6 h. Obtained precipitate was collected, washed,
cobaltites depend upon preparation technique, charge distribution filtrate and then calcined for 4 h at 500 °C to remove organic com­
of charge carrying ions, ion distribution among the tetrahedral and ponents. To get the final product, annealing was done at 800 °C for
octahedral sites, nature of dopant, concentration of dopant etc. [18]. 2 h in an electrical hot air oven.
Choice of proper dopant makes the system applicability more in­ In second step, to get the rare earth doped ZnCo2O4 samples, 10%
teresting. In this work, we have developed a series of rare earth of rare earth oxide powder was mixed well with 90% of prepared
doped ZnCo2O4 nanomaterials (Nd, Sm, Gd, Dy, Y) by adopting a ZnCo2O4 powder and transferred to chrome-steel vial containing
combination of both chemical and physical techniques. It is found 30 milling balls (each having radius ~5 mm) of the same material.
that ionic radius of the rare earth dopant has deep correlation with This sample system was then mounted in a planetary ball mill
structural and electrical properties of the host material. Radius of (Fritsch Pulverisette, P7) for milling at 350 rpm for 1 h. Milling was
the rare earth ions in rare earth oxides (R2O3) are Nd (0.983 Å) > Sm continued with required pause to avoid contamination from the
(0.958 Å) > Gd (0.938 Å) > Dy (0.912 Å) > Y (0.900 Å). Doping of these milling media. Neodymium Oxide (Nd2O3), Samarium Oxide
rare earth cations of different radii brings microstructural changes to (Sm2O3), Gadolinium Oxide (Gd2O3), Dysprosium Oxide (Dy2O3) and
the system and this leads to several modifications in other Yttrium oxide (Y2O3) incorporated ZnCo2O4 samples were prepared
characteristics. In the prepared samples, transition metal ions of the and their nomenclatures were abbreviated as ZCO-Nd, ZCO-Sm,
spinel have unpaired 3d electrons which are interacting with 4f ZCO-Gd, ZCO-Dy and ZCO-Y respectively.
orbital electrons of R2O3 (R=Rare earth) and influence electrical
properties. So, introducing rare earth ions into parent spinel system 2.2. Material characterization
gives rise to 3d-4f couplings which leads to changes in different
physical properties of the system [19]. Rare earth ions preferred to X-ray diffraction patterns of the prepared samples were in­
occupy the octahedral site or B-site of a normal spinel structure as vestigated using Bruker X-ray diffractometer (D8 Advance-AXS)
octahedral site provides them a larger space to be partially sub­ equipped with Ni-filtered CuKα (λ = 1.5414 Å) radiation in a wide
stituted into Co3+ ions. Due to very limited solubility of rare-earth angular range of 15–80 °C. Peak positions of the plotted data were
dopants in normal spinel and inverse spinel structure, concentration compared with Joint Committee of Powder Diffraction System
above maximum solubility limit results formation of an additional (JCPDS) files to ensure the formation of the desired rare earth doped
orthorhombic phase (RCoO3) which hinders the electron transfer ZnCo2O4 nanomaterials. Different structural parameters were ob­
between Co3+ and Co2+ ions [20]. Incorporation of rare-earth ions for served from Rietveld analysis using MAUD (Materials Analysis Using
doping in cobaltite matrix induces lattice strain to the spinel Diffraction) software. For further structural confirmation, Fourier
structure as rare earth ions have larger ionic radii than Co3+, Co2+ and transform infrared spectrums were recorded using Perkin Elmer
Zn2+ ions, so this B-site doping causes structural distortion which spectrometer with KBr standard in the spectral range
significantly change the electrical properties [21]. 400–4000 cm−1. To elucidate the particle size and morphology of the
In our work, XRD confirms absence of any secondary phase leads materials, Field emission scanning electron microscopy (FESEM)
to the fact that we have succeeded in producing single phase rare micrographs and EDX spectrums were recorded by Carl Zeiss
earth doped spinel structure with minimum span of milling time microscope. Shimadzu UV-1800 spectrometer was used to record
under solubility maxima of R2O3. On the other hand, doping rate of UV-Visible absorption spectra of the prepared samples within
success is higher for mechanical methods [22]. In a minimum time 200–800 nm wavelength range. Electrical impedance spectroscopy
span of 1 h, doping of rare earth oxides are successfully done in the (EIS) analysis was carried out using high precession LCR meter
spinel ZnCo2O4. Many literatures available about chemical prepara­ (Model-Agilent) in the frequency range 20 Hz to 2 MHz. For elec­
tion of doped ZnCo2O4 and their application in different fields like trical conductivity measurements, prepared powder samples were
photocatalytic, supercapacitor, gas sensor, biosensor etc. [23–25]. co-axially pressed under 500 MPa pressure using a hydraulic press to
But detailed study on hybrid synthesis of different rare earth doped form a pellet and both sides of the pellets were coated with silver
ZnCo2O4 and their electrical characterization by Mott's VRH model is paste along with copper wire connection.
reported for the first time. Moreover, there are some reports avail­
able about property change of the spinel ferrite system due to 3. Results and discussion
doping of rare earth but to the best of our knowledge, no literature is
reported for dopant radii dependent electrical property correlation 3.1. X-ray diffraction profile analysis and Rietveld refinements
of any spinel cobaltite system yet. To fulfil this research gap, we have
represented this work. Rietveld fitted XRD patterns of rare earth doped and undoped
ZnCo2O4 (1 h milled) samples are shown in Fig. 1. Peak positions of
2. Experiments the Recorded diffraction data are found to be consistent with the
JCPDS file (file No. 23-1390) in the angular range 15°–80°. It confirms
2.1. Synthesis procedure the formation of single phase cubic ZnCo2O4 with space group Fd3m.
For the doped samples, absence of any additional peak reveals the
Rare earth doped ZnCo2O4 nanomaterials were produced in two fact that rare earth dopants are successfully incorporated in the
steps by adopting a hybrid method which combines both physical spinel ZnCo2O4 structure and the spinel structure retains after ball
and chemical method. In the first step, pure cubic ZnCo2O4 was milling. Previous literature shows extra peak or impurity phases are
prepared through simple chemical co-precipitation method. For this, quite common in rare earth doped spinel due to exceeding standard
stoichiometric amounts of analytical grade Manganese acetate [Zn solubility limit. But in our work, 10% of rare earth oxides are suc­
(CH3COO)2,4H2O] (Merck) and Cobalt acetate [Co(CH3COO)2,4H2O] cessfully dissolved into the spinel structure by ball mill with
(Merck) were added with 50 ml de-ionized water in separate bea­ minimum time span (1 h).
kers according to the desired molar ratio 1:2. After stirring for Rietveld refinement with Pseudo Voigt analytical function is
15 min, homogeneous solutions were mixed and poly­ employed for detailed microstructural analysis of the prepared na­
vinylpyrrolidone (PVP) solution (5 molar) added as chelating agent nomaterials using MAUD software (version 2.33) [26,27]. Marquardt
under vigorous stirring for 30 min. At this stage, Ammonia solution least-square procedure was employed for the minimization of the

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B. Mandal, R. Roy and P. Mitra Journal of Alloys and Compounds 879 (2021) 160432

Fig. 2. Variation of lattice parameter and microstrain with different dopant radius.

clearly shows that enhancement in lattice parameter causes decre­

ment in x-ray density. Rare earth R3+ dopant ions replace Co3+ ions in
the octahedral sites which predominate the microstrain depending
on the replacing dopant radii. Model structure of spinel ZnCo2O4
with R3+ substituted octahedral sites are shown in Fig. 3 (green
shaded region represents tetrahedral site and blue shaded region
represents tetrahedral site). For detailed crystallographic insight,
interatomic distances between the ions of tetrahedral (A) and oc­
tahedral (B) sites are computed using the lattice parameter (a)
values with the help of following equations [30,31].

MA MA = a 3 /4 (2)

Fig. 1. Rietveld refined XRD patterns of pure and rare earth doped ZnCo2O4 samples. MA MB = a 11 /8 (3)

MB MB = a 2 /4 (4)
difference between computed (IC) and observed (IO) data. The
background of each XRD profile is fitted using a polynomial of de­ Eqs. (2)–(4) represents interatomic distances between two ions
gree 5 and microstrain is calculated using Popa model. Refined of tetrahedral (A) sites, two ions of tetrahedral (A) and octahedral (B)
outputs depict well matched computed XRD profiles with the ex­ sites and two ions of octahedral (B) sites respectively. From the listed
perimental one. Refinement quality is predicted by the goodness of values of each rare earth doped sample, we can see that values of
fit (GoF) value which is defined by the ratio of weighted residual interatomic distances increase with ionic radii of the dopant ion
error factor (Rwp) and expected error factor (Rexp) and for all the (Table 1). It confirms the rare earth-to-Cobalt substitution in octa­
samples, GoF factor close to unity confirms good quality of refine­ hedral sites of the spinel lattice.
ment [28].
3.2. Fourier transform infrared spectroscopy analysis
GoF = Rwp/Rexp (1)

We get lattice parameter (a), crystallite size (D), average micro­ To identify the molecular compositions and functional group
strain (ε), x-ray density (ρx) and GoF values from Rietveld output and positions, FTIR spectra of all rare earth doped and undoped ZnCo2O4
listed them in Table 1 for all the prepared samples. We can see for samples have been recorded in the wavelength range 400 cm−1 -
doped samples, both lattice parameter and crystallite sizes are in­ 4000 cm−1. This analytical technique is used for infrared radiation
creases with the increasing radii of rare earth dopant (Fig. 2). absorption measurement. Fig. 4 shows sharp bands around
Average crystallite sizes are found to ranging between 25.01 nm (for 3411 cm−1 and 1628 cm−1 due to O-H stretching and H-O-H bending
Y3+ dopant with radius 0.900 Å) to 28.44 nm (for Nd3+ dopant with vibrational mode of entrapped water molecule respectively [32].
radius 0.983 Å). From this result, we can ensure that rare earth ions Absorption bands appearing around 1392 cm−1 and 1103 cm−1 are
successfully incorporated into the system. The linear dependency of attributed to COO functional group and C-O stretching vibration of
the lattice parameter with dopant’s ionic radii and their substitution the carboxylate group [17]. Bands appear around 565 cm−1 and
in the spinel lattice shows it obeys Vegard's rule [29]. Decreasing 671 cm−1 corresponding to the vibrational modes of metal oxide
x-ray density with increasing ionic radius of the rare earth dopant (M-O) bonds presented in the prepared samples. Band position

Table 1
Calculated microstructural parameters of the prepared samples from Rietveld refinement.

Sample Lattice parameter a (Å) Crystallite Size D (nm) Microstrain <ε2> 1/2 Х 10−3 X-Ray Density ρx (gm/cm3) GoF MA – MA (Å) MA – MB (Å) MB – MB (Å)

ZCO 8.145 23.737 4.013 6.230 1.02 3.527 3.377 2.880

ZCO-Y 8.337 25.011 4.291 5.417 1.13 3.610 3.453 2.948
ZCO-Dy 8.682 25.988 5.297 5.151 1.22 3.759 3.599 3.070
ZCO-Gd 8.814 27.013 5.472 4.902 1.19 3.817 3.654 3.116
ZCO-Sm 8.911 27.856 6.398 4.529 1.10 3.893 3.727 3.179
ZCO-Nd 9.200 28.439 6.505 4.002 1.27 3.919 3.752 3.199

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B. Mandal, R. Roy and P. Mitra Journal of Alloys and Compounds 879 (2021) 160432

by reduce the superficial area [20]. Moreover absence of any trace of

secondary phase is also in accordance with the XRD data.

3.4. Energy dispersive X-ray

EDX spectra of the prepared rare earth doped and undoped

ZnCo2O4 samples are shown in Fig. 6. Each spectrum confirms the
presence of constituent major elements of the prepared samples in
their exact positions. As the pellets were coated with gold before
taking the FESEM and EDX spectra, peak of Au is also present in the
figures. Rare earth incorporated host ZnCo2O4 samples confirmed no
extra element is present in the energy spectra. Weight percentage
and atomic percentage of all elements of the samples are given in
the inset of the figures. Percentages are found very close to expected
values which confirm desired stoichiometry is achieved for all rare
earth doped samples.

Fig. 3. Model structure of spinel ZnCo2O4 with R3+ substituted octahedral site (green
3.5. UV-Vis spectroscopy
shaded region represents tetrahedral site and blue shaded region represents octa­
hedral site).
Optical band gap of the prepared rare earth doped ZnCo2O4
samples are estimated from the Tauc's equation [30] given by,

( h )n = k (h Eg) (5)

where α is the absorption coefficient, hν is energy of incident photon,

Eg is the band gap energy and k is a material dependent pro­
portionality constant and n is electronic transition dependent power
index. Value of n is 1/2 and 3/2 for allowed and forbidden indirect
interband transition and it is 2 and 3 for allowed and forbidden di­
rect interband transition. Bang gap energy values are calculated by
intersecting the baseline of (αhν)2 vs. hν plot (shown in Fig. 7) by
extrapolating the band line where (αhν)2 becomes zero. Estimated
values of band gap energies for ZCO-Nd, ZCO-Sm, ZCO-Gd, ZCO-Dy
and ZCO-Y are ~3.48 eV, ~3.62 eV, ~3.77 eV, ~3.89 eV and ~3.99 eV
respectively. This narrowing of band gap energy values with in­
creasing dopant radii might attributed to the electron confinement
process and/or due to microstructural changes and introduction of
defect states in the lattice structure.

3.6. Electrical properties

Fig. 4. FTIR spectra of the rare earth doped ZnCo2O4 samples. 3.6.1. Impedance spectroscopy
To explore the relationship between microstructural and elec­
−1
around 671 cm corresponds to stretching vibrational modes of trical properties of the prepared rare-earth doped ZnCo2O4 samples
Zn-O bond at tetrahedral sites and 565 cm−1 corresponds to Co–O and their applicability as electrolyte material in SOFC, Complex
bond at octahedral sites of the host ZnCo2O4 sample [30]. Slight Impedance Spectroscopy (CIS) was employed in the temperature
shifting of bands positions from the undoped ZnCo2O4 sample was range 353–453 K. Fig. 8(a) shows temperature dependent Nyquist
observed due to change in reduced mass of the system caused by plots for Neodymium doped ZnCo2O4 sample and Fig. 8(b) shows the
substitution of rare earth ions in the octahedral site of the host same for all five Rare Earth doped samples at a fixed temperature
ion [33,34]. 433 K. Both the plots depict depressed semi-circular arcs having
their centers at negative y-axis. This type of nature indicates non-
Debye type relaxation phenomena of the prepared samples [35].
3.3. Field emission scanning electron microscopy analysis Each cut point in x-axis by the semi-circular arc represents its re­
sistance at particular temperature. Fig. 8(a) shows resistance de­
FESEM micrographs of the as prepared ZnCo2O4 sample and rare creases with increasing experimental temperature, which confirms
earth doped ZnCo2O4 samples are shown in Fig. 5. Each micrograph semi conducting nature of the prepared nanopowders and Fig. 8(b)
shows well distributed spherical particles in the cluster. As the shows resistance increases with increasing radius of the dopant.
doped samples are prepared through ball milling, particle size of the Nyquist plot consists of three overlapping semi-circular arcs. High-
same are much smaller than undoped chemically prepared ZnCo2O4 frequency arc corresponds to intra-grain contribution, intermediate-
material. Estimated average grain sizes from Image J software vary frequency arc corresponds to grain boundary contribution and low-
from ~27.21 nm (for Y3+ doped) to ~30.33 nm (for Nd3+ dopant) frequency arc represents the electrode-ceramic interface contribu­
which are slightly larger than the estimated size from Rietveld tion (negligible). According to Brick-layer model, both grain and
output. This is due to the fact that XRD gives us the crystallite size, grain boundaries have different contributions for polycrystalline
whereas from SEM, we get the sizes of grains formed by agglom­ materials [36]. We have fitted our experimental arcs using EC-Lab
eration of large number of crystallites. This agglomeration of nano­ software with a circuit (shown in the inset of Fig. 8(a)). The circuit is
particles occurs due to their tendency to achieve lower energy state designed as series combination of parallelly connected resisters

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B. Mandal, R. Roy and P. Mitra Journal of Alloys and Compounds 879 (2021) 160432

Fig. 5. FESEM images of (a) as prepared ZnCo2O4 (b) ZCO-Y (c) ZCO-Dy (d) ZCO-Gd (e) ZCO-Sm and (f) ZCO-Nd.

(grain and grain boundary) and constant phase elements (grain and C = Q1/ aR1/ a 1 (7)
grain boundary). From fitting, we get grain and grain boundary re­
The exponent (a) value lies between zero to one indicating non-
sistances (Rg and Rgb) and grain and grain boundary phase elements
Debye type relaxation phenomena. We have calculated conductivity
(Qg and Qgb) by the equation [37,38],
value using the equation [17],
Z * ( ) = [Rg / Rg Q g (j )ag + 1] + [Rgb/Rgb Q gb (j )agb + 1] (6) = l /RA (8)
where l, R and A denotes width, resistance and area of the experi­
Q represents deviation of capacitance from ideal behavior.
mental pellets of each sample. Equivalent resistance values
Capacitance value can be calculated using the equation [37],
(combination of grain and grain boundary resistances) along with

Fig. 6. EDX spectra of (a) as prepared ZnCo2O4 (b) ZCO-Nd (c) ZCO-Sm (d) ZCO-Gd (e) ZCO-Dy and (f) ZCO-Y.

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B. Mandal, R. Roy and P. Mitra Journal of Alloys and Compounds 879 (2021) 160432

regions separated by crossover frequency (ωH). Frequency in­

dependent zone for ω < ωH referred as dc conductivity and the zone
for ω > ωH referred as ac conductivity. Dc conductivity is a result of
continuous successful hopping of mobile charge carriers between
two allowed localized sites and ac conductivity at higher frequency
side arises due to dispersion of mobile charge carriers [30]. At high
frequency region, both successful and unsuccessful hopping may
occur. But with the increasing ratio of successful to unsuccessful
hopping, dispersion between the allowed states increases. Hopping
from one site to another represents transition between long range
hopping to short range carrier mobility [32]. This type of con­
ductivity nature obeys Jonscher power law [40],

= +A n (10)
dc

where σdc, A and n denotes dc conductivity, pre-exponential para­

meter and frequency exponent respectively. Almond-West relation is
used to fit the conductivity curves using the equation [41],

( )= n]
Fig. 7. Tauc’s plot of the rare earth doped ZnCo2O4 samples. dc [1 +( / H) (11)

We get the fitting parameters for compositional curves i.e. dc

the calculated conductivity values are listed in Table 2 for a parti­
conductivity value, hopping frequency value and frequency ex­
cular experimental temperature.
ponent value and listed them in Table 2. With the increase in tem­
We can see that, resistance value decreases and conductivity
perature, conductivity increases from 0.666 × 10−4 Ω−1cm−1 to
value increases with decreasing radius of the dopant in the spinel
0.823 × 10−3 Ω−1cm−1 for ZCO-Gd, as increasing temperature helps
structure. Electrical transport properties of the nano spinels are
the charge carriers to gain sufficient energy to overcome the barrier
predominant by the grain boundary than the grain interior itself as
[42]. Dc and ac conductivity increases with increasing temperature,
grain boundary consist of various impurities [18]. So grain boundary
indicating thermally activated process as well as negative tempera­
exhibits higher resistivity and it blocks the migration of the charge
ture coefficient of resistance (NTCR) of the nanomaterial character­
carriers. Grain boundary blocking factor (αgb) for all the samples are
ising semi-conducting nature [33]. For the compositional curves,
calculated using the equation [39],
fitting parameter indicates dc conductivity and hopping frequency
gb = Rgb/Rg + Rgb (9) increases with the decrease in particle size which is consistent with
the result of Nyquist plot. Micro mechanism of the doped systems
Blocking factor increases from 0.53 for ZCO-Y to 0.72 for ZCO-Nd indicates better mobility of the smaller charge carriers. Crystallite
(calculated from the fitting parameters) which is responsible for size increases due to hindered crystal growth of dopant radius which
reducing the conductivity. It clearly indicates that for smaller par­ preferred to occupy octahedral space by replacing Co3+ ions. It
ticle size, charge carriers crossover the activation barrier as inter- causes lattice strain. For smaller ions, dispersion becomes easier due
granular hopping distance decreases. Thus increment in mobility of to their decreasing hoping distances. With the increasing octahedral
the charge carriers increases the conductivity of the nanomaterial. lattice stain, obstacle of the migration path causes trimmed up
mobility. So the conductivity increases with decreasing lattice strain
3.6.2. Conductivity mechanism due to relaxation of the system [17].
Fig. 9(a) shows frequency dependent complex ac conductivity The n value generally lies between 0 and 1 but it can have values
spectra of ZCO-Gd in the temperature range from 353 K to 433 K and greater than 1 depending on the interaction between migrated ions.
Fig. 9(b) depicts compositional conductivity curves for all the rare Different models are available based on classical (hopping of charge
earth doped samples at 433 K. Conductivity curves show two distinct carriers) and quantum mechanical (tunneling of charge carriers)

Fig. 8. (a) Temperature dependent Nyquist plot for ZCO-Nd (b) compositional Nyquist plots at 433 K (Inset of Fig. 8(a) shows the equivalent fitting circuit).

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B. Mandal, R. Roy and P. Mitra Journal of Alloys and Compounds 879 (2021) 160432

Table 2 [20]. As bond energy of R3+- O2- is larger than Co3+- O2-, R3+ sub­
Different fitting parameters from conductivity curves. stitution to octahedral space and formation of R3+- O2- bond needed
Sample σdc × ωH (rad/sec) n R (= Rg + Rgb) Ω σ (=l/RA) × more energy. So Rare Earth substituted cobaltites have higher
10−3 Ω−1cm−1 10−3 Ω−1cm−1 thermal stability than pure cobaltite system [44].
ZCO-Y 1.151 5.859 × 106 0.89 187.42 1.039 Reciprocal temperature dependence of the frequency in­
ZCO-Dy 1.025 5.158 × 106 0.71 212.50 0.917 dependent dc conductivity for all the prepared samples are shown in
ZCO-Gd 0.823 4.936 × 106 0.65 236.44 0.824 Fig. 10(b). It obeys Arrhenius equation,
ZCO-Sm 0.716 4.610 × 106 0.61 284.82 0.684
4.094 × 106 = 0 exp( Ea/KB T )
ZCO-Nd 0.495 0.53 415.91 0.468 (13)
dc

where, σ0, kB and Ea represents the pre exponential factor, Boltz­

point of view [43]. According to increment or decrement of n with mann constant and activation energy for conduction mechanism
increasing temperature, small polaron hopping mechanism or Cor­ respectively. Obtained dc conductivity values by fitting the con­
related Barrier Hopping (CBH) mechanism is applicable. If n de­ ductivity isotherms for all the samples gives the Arrhenius slope.
creases with increasing temperature upto a certain value then Slope values of the least-square linear fits are used to calculate the
increases then conduction mechanism follow Overlapping Large activation energy. Variations of dc conductivity and corresponding
Polaron Tunneling (OLPT) model. For our samples, increment of n activation energies with different dopant radius are represented in
with increasing temperature indicates small polaron hopping me­ the inset of Fig. 10(b). It is seen that the activation energy gradually
chanism. increases with decreasing conduction efficiency of the doped sam­
To understood small polaron hopping among the localized sites ples. This indicates lowering of activation barrier causes increasing
in Rare Earth doped ZnCo2O4 samples, plots of log(σ'-σdc) vs. log(ω2) mobility of the charge carriers. It is also clear from the figure that
for all the samples at 433 K are shown in Fig. 10(a). Frequency de­ lowering of barrier potential for conducting charge carriers imparts
pendent conductivity due to small polaron hopping mechanism high mobility with reduced activation energy for electrical
obeys the relation [33], conduction.
Electrical data was further analysed using Variable Range
= 2 /1 + 2 2
dc (12) Hopping model proposed by Mott. As Mott’s VRH model is con­
sistent with our previously discussed ac conductivity formalism, so
where ω and τ represents angular frequency and relaxation time.
this model helps to understand transport mechanism of the ther­
Approximated ω2τ2 ≪ 1, above plots must show a linear relationship
mally activated polarons through tunneling between occupied to
for small polaron hopping. Our experimental data satisfied the
unoccupied localized states [45]. Temperature dependent resistivity
condition for all the samples, so the prepared samples clearly sup­
relation can be represented as [46],
port the small polaron hopping conduction mechanism.
Strong hybridization of 4 f state of Rare Earth ions with 3d state 1
TM 1+d
of transition metal explains enhanced conductivity of the rare earth dc = 0 exp
T (14)
doped spinel systems. Conductivity increases with increasing fre­
quency as it acts as a pumping force which helps to push the charge where ρdc, ρ0, d and TM are dc resistivity, pre-exponential factor,
carriers between allowed localized sites [1]. Electron hopping be­ dimensionality and Mott's characteristic temperature of the pre­
tween Co2+ and Co3+ in the octahedral space and hole hopping be­ pared materials. For three-dimensional system, d = 3. So Eq. (14) can
tween Zn2+ and Zn3+ ions in tetrahedral space contribute to be represented as,
conduction mechanism due to their 3d spin coupling [16]. By in­
1
troducing Rare Earth in the system, 3d-4 f coupling profound to TM 4
enhances the conductivity. This hopping mechanism explains the dc = 0 exp
T (15)
conductivity behavior of the system properly. Moreover semi-con­
ducting nature of cobaltites can be explained by Verwey's hopping Mott’s characteristic temperature TM depends on the electronic
model as conductivity mainly depends on the availability and mo­ structure of the system and is represented as,
bility of the charge carriers. When R3+ ions substituted Co3+ ions,
number of hopping pairs increases and Co3+ energy level shifts to­ CM
TM = ( )3 (K)
wards Zn3+ level resulting enhanced hopping between Co2+ and Co3+ N (EF ) KB (16)

Fig. 9. (a) Temperature dependent complex ac conductivity spectra of ZCO-Gd (b) compositional conductivity curves at 433 K.

7
B. Mandal, R. Roy and P. Mitra Journal of Alloys and Compounds 879 (2021) 160432

Fig. 10. (a) Plots of log(σ′- σdc) vs. log(ω2) for all the doped samples at 433 K (b) Arrhenius plots of the samples (inset shows variations of dc conductivity and corresponding
activation energies with different dopant radius).

where N(EF) represents density of state (DOS) at Fermi energy, KB is

the Boltzmann constant, 1/γ is decay length of localized polaron
wave function (~0.83 Å as it is approximately equal to Bohr radius)
and CM is a constant. There are different approximations about the
constant value to express the VRH parameters. According to Godet,
CM ~310 for the materials having exponentially distributed N(EF), but
according to Mott, CM ~16 × (3/2π) [47]. So according to Mott's VRH
model, Mott's temperature is represented as,

24
TM = ( )3 (K)
N (EF ) KB (17)

With the obtained value of N(EF), Polaron Hopping length (R) and
polaron hopping energy (W) are calculated by the relations [48],
1/4
9 1
R= (cm)
8 TN (Ef ) KB (18)

3
W= (ev) Fig. 11. Plots between ln (ρdc) and T−1/4 for the rare earth doped samples.
4 R3N (Ef ) (19)
Temperature dependent hopping distance may greater than the
To apply Mott's VRH model, there are some prerequisite conditions,
distance between two neighboring sites at low temperature due to
lower activation energy involvement [33]. Hopping energy of ther­
1. Linear relationship between ρ and T−1/4
mally activated polarons also decreases with decreasing radius of
2. Value of localization parameter, N(EF)/γ3 eV varies between 1
rare earth ions, which is in agreement with the activation energies
and 10−5
(Ea) of the systems (calculated from Arrhenius equation). So it in­
3. Polaron hopping range Rγ > 1
dicates dc conductivity is associated with polaron hopping inside the
4. Polaron hopping energy W > KBT (0.026 eV at 300 K)
long range potential well. Variation of DOS at Fermi level and acti­
vation energy of the systems with dopant radius was found to vary
Now, TM is calculated from the slope of the plot between ln (ρdc)
inversely with each other.
and T−1/4 (shown in Fig. 11) which shows linear relationship. Hop­
ping length and hopping energy values are calculated using these TM
values. Calculated Mott parameters for all prepared samples are 3.6.3. Dielectric loss factor
listed in Table 3 and found to satisfy the required conditions for their Conduction mechanism of the prepared Rare Earth doped spinel
applicability in M-VRH model. systems are interrelated with the dielectric loss factor which is
Increasing N(EF) values with decreasing dopant radius is ob­ strongly affected by microstructural parameters, mobility of oxygen
served in accordance with the previously measured conductivity ions, defect sites etc. Fig. 12(a) represents frequency dependent di­
values of the prepared systems. This similarity confirms the corre­ electric loss tangents for the sample ZCO-Dy at different tempera­
lation between conductivity of the materials and DOS at Fermi level. tures from 353 K to 433 K and Fig. 12(b) represents frequency
Generation of donor states are responsible for increasing trend of N dependent compositional dielectric loss tangents at 433 K. Intensity
(EF) with dopant ion decrement. It is also attributed to conductivity of the loss tangent have maximum value when the externally ap­
increment of the system. So, variation of different Mott's variable plied field is approximately equal to the hopping frequency of the
with different rare earth dopant reflects on the conductivity beha­ charge carriers and it gradually decreases to a constant value at
vior of the prepared system. Polaron hopping distance decreases high-frequency region. This saturation behaviour concludes that the
with decreasing ionic radius of dopant cations in the spinel system. reorientations of electric dipoles are independent of temperature at

8
B. Mandal, R. Roy and P. Mitra Journal of Alloys and Compounds 879 (2021) 160432

Table 3
Estimated parameters of Mott’s VRH model and activation energies from Arrhenius plots.

Sample TM × 109 (K) N (EF) J−1m−3 N (EF)γ−3 eV R (Å) Rγ W (eV) Ea (eV)

44 −4
ZCO-Nd 3.119 3.103 × 10 0.284 × 10 21.93 0.077 0.455 0.446
ZCO-Sm 2.974 3.254 × 1044 0.298 × 10−4 21.67 0.078 0.450 0.440
ZCO-Gd 2.270 4.263 × 1044 0.391 × 10−4 20.26 0.075 0.420 0.411
ZCO-Dy 1.975 4.899 × 1044 0.449 × 10−4 19.56 0.075 0.406 0.397
ZCO-Y 1.101 8.788 × 1044 0.805 × 10−4 17.06 0.068 0.345 0.343

Fig. 12. (a) Temperature dependent dielectric loss tangents for the sample ZCO-Dy (b) compositional dielectric loss tangents at 433 K.

high frequency field. Relaxation peak of the loss tangents are in­ impedance spectra of ZCO-Nd has been studied. Fig. 13 shows ex­
creasing with increasing temperature indicating thermally activated perimental frequency (ω) is scaled by the hopping frequency (ωH)
process. For compositional plots, it is clear that intensity of the loss and impedance axis is scaled by Zmax. Scaled spectra of impedance
factor increases with decreasing dopant radius at low-frequency isotherms at different measuring temperatures were found to be
region as a result of more and more hopping of mobile charge car­ completely merged into a single master curve. The spectra clearly
riers. This concept of high loss factor with reduced resistivity can be indicates that the samples obey time-temperature superposition
explained by Koop's phenomenological model [49]. According to this principle (TTSP) represented by the following equation [32],
model, smaller grains results in faster charge conduction and both
conduction mechanism and loss-factor behavior are correlated to Z ( )/Zmax = F ( / H) (20)
each other [17].
So, it is clear from our observation that ln(ρ) - T−1/4 relation for where F is a scaling function, which is independent of both the
our fabricated compounds provides an excellent tool to examine the measuring temperature and dopant radius of the ZnCo2O4 spinel
mechanism of the variable range hopping conduction. system. Some deviation in the master plots in higher frequency re­
gions is observed due to window effect [30]. So the conductivity
3.6.4. Scaling mechanism mechanism is only associated with the number of mobile charge
To understand the dependence of temperature on the conduction carriers which changes with the measuring temperature and doping
mechanism, scaling behavior of real (Z′) and imaginary (Z″) part of concentration without changing the conduction mechanism.

Fig. 13. Scaled spectra of ZCO-Nd for (a) Z′ and (b) Z″.

9
B. Mandal, R. Roy and P. Mitra Journal of Alloys and Compounds 879 (2021) 160432

4. Conclusion measurements. The authors also acknowledge Dr. A. Dutta,

Department of Physics, The University of Burdwan for providing
In this work, pure spinel structured ZnCo2O4 nano-cobaltite ma­ instrumental support.
terial has been fabricated successfully via co-precipitation method
and then a series of rare earth doped (Nd, Sm, Gd, Dy, and Y) ZnCo2O4 References
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