Metallic magnetism and change of conductivity in the nano to bulk

transition of cobalt ferrite

A. Arunkumar, D. Vanidha, K. Oudayakumar, S. Rajagopan, and R. Kannan

Citation: J. Appl. Phys. 114, 183905 (2013); doi: 10.1063/1.4829923

View online: http://dx.doi.org/10.1063/1.4829923
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 JOURNAL OF APPLIED PHYSICS 114, 183905 (2013)

Metallic magnetism and change of conductivity in the nano to bulk

transition of cobalt ferrite
A. Arunkumar,1 D. Vanidha,1 K. Oudayakumar,2 S. Rajagopan,3 and R. Kannan1,a)
1
Department of Physics, Pondicherry Engineering College, Puducherry–605 014, India
2
Department of Physics, Sri Manakula Vinayagar Engineering College, Puducherry–605 107, India
3
Department of Chemistry, Pondicherry Engineering College, Puducherry–605 014, India
(Received 2 May 2013; accepted 26 October 2013; published online 12 November 2013)
Variations in conductivity with particle size have been observed in cobalt ferrite, when
synthesized by solgel auto-combustion method. Impedance analysis reveals metallic and
semiconducting behavior at room temperature for a particle size of 6 nm and 52 nm, respectively.
Upon thermal activation, metallic to semiconducting phase transition has been observed as a
function of particle size and vice-versa. Grainboundary Resistance (Rgb), increased drastically
with particle size (19 MX for 6 nm and 259 MX for 52 nm) at room temperature. AC conductivity
and dielectric constants exhibit similar metallic to semiconducting phase transition at 6 nm and
semiconducting behavior at 52 nm with temperature in the selected frequencies. Enhanced
magnetic moment with an increase in the grain size along with decreased coercivity (1444 G to
1146 G) reveals transition from single domain to multi-domain. Increased inter-particle
interaction is responsible for metallicity at the nano level and on the contrary semiconductivity is
C 2013 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4829923]
attributed to bulk. V

INTRODUCTION magnetization and enhanced coercivity to annealing induced

grain growth and segregation, respectively. Increase in the
Cation distribution plays an important role in the proper-
quenching temperature is also found to increase the saturation
ties of bulk ferrite compared to the nano phase.1 Ferrite is
magnetization.11 Owing to thermal aging, Templeton et al.22
represented by the chemical formula AB2O4, whereas A-site
reported the conversion of normal spinel into an inverse spinel
is tetrahedral and B-site is octahedral. If divalent ion occu-
from Mossbauer studies.
pies only in A-site, it is called normal or else if it occupies
The strength of c-c and c-a-c interaction is a measure of
both A and B-sites, the spinel is mixed. Further, the cationic
distribution of the cations among tetrahedral and octahedral
exchange is measured by the number of divalent ions in the
sites, which in turn is related to TC.10,14 Iqbal et al.15 reiter-
octahedral sites.2 Cation distribution in ferrites can be of
ated that the TC represents the strength of the magnetic inter-
equilibrium or non-equilibrium in nature.3,4 For every A to B
action between the cation spins. Additionally, an increase in
migration, there will be a corresponding B to A migration in
the number of magnetic ions in the A-site, on mechanically
order to maintain the equilibrium of charge and stabilization
milled Nickel Zinc ferrite, is found to exhibit surface spin
of cubic phase, which is normally found in all the bulk mate-
effect which affects the Curie temperature, as reported in the
rials. Chemical substitution, ionic radius of the dopant atom,
Mossbauer and EXAFS studies.23
variations in synthesis,5,6 and annealing were used to alter
Occasionally, lattice diffusion is also found to change
cation distribution in the bulk materials. Non-equilibrium
the cation distribution. Doping induced lattice diffusion
cation distribution found in nano materials with large surface
increases the diffusion length categorically modifying the
to volume ratio, gives rise to anomalous properties in the
cation diffusion in the Ce doped NiFe2O4.13 Philip et al.17
nano ferrite.3,7,8
experimentally demonstrated that the strain can also be a
The cation distribution is expected to affect the magnet-
cause of cation redistribution among tetrahedral and octahe-
ization via cation-cation (c-c)/cation-anion-cation(c-a-c) or
dral sites in ferrites. Partial cation inversion is found to be re-
A-B exchange interaction, electrical conductivity, magnetic
sponsible for unusual high coercivity as a result of acidic
anisotropy, Curie temperature (TC), and the magnetostriction
treatment of cobalt ferrite.24
coefficient of the material.9,10 Cation migration can be
In nanoferrites, net magnetization is measured not only
enabled by thermal effects like annealing and quenching,11
from the difference between A and B sub-lattice magnetization
particle size,12 lattice diffusion,13 preparation condition,2
but also from the surface-to-volume ratio induced surface spin
namely, reduction reaction leading to reduction in the Fe
effect. In the case of reduced particle size, the magnetization
content at B-site,6,14,15 pressure,16 and strain.17,18
contribution arising from the surface atom dominates the
With increasing annealing temperature, the average parti-
degree of inversion. But when the particle size is very large,
cle size increases, which in turn increases the magnetization
the surface contribution drops and magnetization become the
due to cation reordering.19,20 Lee et al.21 recorded increased
function of inversion only.2,25,26 On the contrary, reduction in
the magnetic moment compared to the theoretical value is
a)
Author to whom correspondence should be addressed. Electronic mail: attributed to presence of noncollinear spin structure due to
kannan@pec.edu. Tel.: þ 91 9442787484. Fax: þ91 413 2655101. nano nature of the system.27 Unfortunately, there are no proper

0021-8979/2013/114(18)/183905/7/$30.00 114, 183905-1 C 2013 AIP Publishing LLC

V
183905-2 Arunkumar et al.
FIG. 1. XRD pattern of cobalt ferrite sintered at 400  C and 800  C.
experimental probes for quantification of surface contribution,
even though many of the reports have been quoted on this
effect.
Tung et al.28 have come across a very high magnetiza-
tion of 67.95 emu/g (at 2 K) lower than bulk CoFe2O4
(80.8 emu/g). Inspite of increase in the surface to volume ra-
tio, the decrease in the magnetization is attributed to the
presence of surface spin moments due to smaller particle
size (3.3 nm). Cannas et al.2 reported the variation in mag-
netic properties inspite of nearly constant cation distribution
and independent of particle size (6–28 nm). This indicates
the presence of surface spin contribution in silica coated
cobalt ferrite.
Cation distribution affects not only the magnetization
but also the electrical properties by means of strain and
increased resistance. Epitaxial strain due to doping has a
direct effect on the size of the bandgap leading to an emperi-
cal correlation between band width and cation inversion.18
Moreover, Iqbal et al.15 traced the increase in the electrical
resistance and decrease of dielectric constant to the weaken-
ing of A–B magnetic exchange interaction (domination of
B-B) arising out of cation reordering. Independently, metal
like behavior is observed in the transport properties of the
system. Besides, after a detailed study for the absence of
impurity phases, L€ uders et al.14 attributed metallic nature to
either RKKY (Ruderman-Kittel-Kasuya-Yosida) or Zener’s
double exchange magnetic interaction.
Various authors have20,29,30 reported semiconducting to
metallic phase transition in ferrites whereas Kannan et al.31
reported inversely in cobalt ferrite. Apart from this, in our
case, cobalt ferrite exhibits single domain, superparamagnetic
behavior at the nano level and multi-domain, bulk nature at
increased particle size. Henceforth, the origin of metallicity
is connected to superparamagnetism and semiconducting
TABLE I. Particle size, lattice parameter (a), magnetization (M), and coercivity (Hc) of CoFe2O4.
Sample Sintering temperature ( C) Particle size D (nm)
CoFe2O4 400 6.54
800 51.19
J. Appl. Phys. 114, 183905 (2013)
behavior to bulk nature, converging to c-c/c-a-c enabled
exchange interaction.
PREPARATION
CoFe2O4 was prepared by sol-gel auto-combustion tech-
nique using stoichiometric amounts of analytical grade iron
nitrate (Fe (NO3)39H2O), cobalt nitrate (Co (NO3)26H2O),
and citric acid (C6H8O7). Aqueous metal nitrate solutions
were added sequentially to the chelating agent (citric acid)
drop wise under constant stirring.32 Ammonia solution was
slowly added to the above mixture and the pH value was
adjusted at about 9 for metal complexing. The mixture was
continuously stirred by a magnetic stirrer at 80  C on a hot
plate till aerogel was formed. Continued heating resulted in
auto-combustion to form a fluffy powder and the resultant
product was ground well and sintered at two different tem-
peratures 400  C and 800  C.
Prepared ferrite samples were characterized by PXRD
using XPERT-PRO X-ray Diffractometer. Room tempera-
ture M–H curve was obtained from vibrating sample magne-
tometer (VSM) using Lakeshore, Model: 7404 at CIF,
Pondicherry University. Impedance analysis was carried out
using LCR meter (HIOKI) in the frequency range 42 Hz to
5 MHz.
XRD STUDIES
Fig. 1 represents the XRD pattern of CoFe2O4 sintered
at 400  C and 800  C, confirm single phase formation of a
spinel cubic. The average crystallite size is calculated from
Scherer’s formula.33 Average particle size increases as the
sintering temperature increases, following the linear grain
growth due to homogeneity at the grain boundary.34,35
Lattice parameter is determined from the XRD data and
listed in Table I. The average particle size of the cobalt fer-
rite is 6 nm when the sintering temperature is 400  C. When
the sintering temperature is increased to 800  C, the average
particle size becomes 52 nm indicative of bulk nature.4,36
The lattice parameter (a) increases from 8.36 Å to 8.46 Å as
the sintering temperature along with the average particle size
increase.37
IMPEDANCE STUDIES
Impedance measurements have been carried out for
the samples at selected temperatures in the frequency
range 42 Hz to 5 MHz. The Nyquist plots corresponding to
CoFe2O4 of 400  C and 800  C sintered exhibit only one
semicircle as shown in Fig. 2. The results suggest that the
grain boundary contributed conductivity of high resistance
without any electrode effect. Rgb(diameter of the semi-
circle)38 is found to increase with increase in temperature
Lattice parameter (a) Å Magnetization (M) (emu/g) Coercivity Hc(G)
8.3666 22.401 1444.3
8.4651 46.040 1146.3
183905-3 Arunkumar et al.
FIG. 2. Nyquist plots of cobalt ferrite sintered at 400  C and 800  C.
as shown in Fig. 3(a), reaching a maximum and then
decreases indicating that the system has undergone metallic
to semiconducting transition accompanied by the transfor-
mation from grain boundary conduction to grain conduction
(since grain boundary volume is higher than grain vol-
ume).39 Increased electron energy is responsible for the dis-
appearance of grain boundary conduction and appearance
of grain conduction due to thermal activation. This transi-
tion occurs at 364 K for 400  C sintered sample (6 nm).
Semiconducting nature was observed with thermal treat-
ment, in which Rgb was found to decrease indicating parti-
cle size induced phase transition for 800  C sintered
sample.40 As a function of temperature, Rgb reaches mini-
mum (Fig. 3(a)) and further metallicity was not found due
to the limited nature of temperature measurement and may
become metallic at higher temperature.
The activation energy (Ea) is obtained, by fitting the dc
conductivity data of the Rgb values, using an Arrhenius rela-
tion r ¼ r0 exp (Ea/kBT), where r0 is pre-exponential fac-
tor with dimension of (X cm)1 and kB is the Boltzmann
constant41 and is tabulated in Table II. It is found that the
slope changes from positive to negative with the increase in
temperature (Fig. 3(b)), indicating metallic to semiconduct-
ing transition for 400  C sintered sample. Only semiconduct-
ing nature with negative slope is observed for 800  C
sintered sample.42
The existence of positive slope confirms metal like na-
ture. Goodenough43 attributed metallicity to various reasons,
namely, nonstoichiometry, increase in the resistance before Tc
and c-c interaction through covalent bond which is a function
of critical cation separation. Furthermore, Wu et al.44 have
TABLE II. Activation energy of the cobalt ferrite obtained from impedance analysis, ac conductivity, and dielectric constant.
Impedance (meV)
CoFe2O4 Metallic Semiconducting

Sintered at 400 C 203.2 526.5
Sintered at 800  C … 453.3
J. Appl. Phys. 114, 183905 (2013)
FIG. 3. (a) Variation of Rgb with temperature for CoFe2O4 sintered at
400  C and 800  C. (b) Calculation of Activation energy from ln r (S cm1)
vs 1000/T of CoFe2O4 sintered at 400  C and 800  C.
quoted Chen’s theory45 of electrical conductance leading to
metallicity when the distance between the nanoparticles is in
the quantum relative region.
Hence, when the particle size is very small, c-c interac-
tion dominates, giving rise to metal like nature41,43 at room
temperature for 400  C sintered sample. As the sintering
temperature is increased to 800  C, the particle size increases
and the c-a-c interaction dominates over c-c giving rise to
semiconducting nature which was commonly found in all the
ferrites at room temperature.20,29–31
AC CONDUCTIVITY ANALYSIS
The frequency dependent ac conductivity measured at
different temperatures, for the sample sintered at 400  C and
800  C is shown in Fig. 4. The conductivity almost remains
the same at low frequency and increases strongly at high fre-
quency exhibiting dispersion. The dc to ac changeover takes
place in the frequency range of 103 Hz to 107 Hz with tem-
perature.46 Conductivity is found to decrease with increase
in temperature, reaching to a minimum and then increases
for 400  C sintered sample. On the contrary, conductivity
increases continuously with temperature for 800  C sintered
sample as shown in Figs. 5(a) and 5(b). A clear shift in the
dispersion behavior as a consequence of nano to bulk change
was found as indicated in Fig. 4.47
The ac conductivity of the system can be explained on
the basis of the expression41
rac ¼ r1 ðTÞ þ r2 ðx; TÞ
Activation Energy
Ac conductivity (meV) Dielectric (meV)
Metallic Semiconducting Metallic Semiconducting
216.4 569.9 340.7 550.7
… 472.2 … 485.2
183905-4 Arunkumar et al.
FIG. 4. Variation of ac conductivity with frequency for CoFe2O4 sintered at
400  C and 800  C.
where r1(T) is due to band conduction and is related to
dc conductivity which is temperature dependent. r2(x, T)
represents hopping conduction which occurs among the octa-
hedral B-sites and it is both temperature and frequency
dependent.41
Non-equilibrium site occupancy is one of the remarkable
characteristics of nanostructured materials. The occupation
index of A and B-sites strongly depends on the synthesis con-
ditions like particle size, temperature, strain, and pressure.
The transition between Fe2þ $ Fe3þ/Co2þ $ Co3þ/Co2þ
þ Fe3þ $ Co3þ þ Fe2þ ions might be responsible for con-
duction in ferrite due to hopping of charge carriers between
adjacent octahedral sites. Reduction reaction (Fe3þ to Fe2þ)
and the (Fe2þ/Fe3þ) ratio control the overall conductivity in
ferrite materials.15
Temperature dependent hopping is represented by the
Arrhenius equation r1T ¼ r0 exp (Ea/kBT), where Ea is the
activation energy and r0 is pre-exponential factor.
Activation energy was calculated from ln r1 T versus 1000/T
plot, where the slope change from positive to negative as
FIG. 5. Temperature dependence of rac at selected frequencies of the
CoFe2O4 sintered at (a) 400  C and (b) 800  C. (c) Calculation of activation
energy from ac conductivity (ln racT (S cm1 K) vs 1000/T) for the CoFe2O4
sintered at 400  C and 800  C.
J. Appl. Phys. 114, 183905 (2013)
FIG. 6. Variation of “n” with Temperature of CoFe2O4 sintered at 400  C
and 800  C.
shown in Fig. 5(c) for the sample sintered at 400  C whereas
only negative slope is observed for 800  C sintered sample.41
Hence experimentally observed positive slope is attributed to
metallicity and negative slope to semiconducting nature.
When the particle size changes (6 nm to 52 nm) from nano to
bulk, the corresponding activation energies are found to vary
significantly from 569.9 meV to 472.2 meV due to changes
in the mobility associated with the modifications in the grain-
boundary configuration.40 The phase transition due to ther-
mally activated process was found to be in agreement with
impedance analysis as discussed earlier.
Frequency dependent ac conductivity is given by
Jonscher’s universal conduction mechanism48
r2 ðx; TÞ ¼ BðTÞxn ðTÞ
where “n” is the dimensionless parameter obtained from the
slope of log (rac) versus log (x). The frequency dependent
hopping conduction is further analyzed based on the varia-
tion of “n” with temperature as explained in our previous
work.31
The value of “n” increases with increase in temperature
and then decreases, thereby indicating small polaran hopping
(SPH) followed by correlated barrier hopping (CBH) as
shown in Fig. 6 for 400  C sintered sample. In support to our
argument, a similar trend was reported by Farea et al.49
Independently, transition from SPH to CBH occurring at a
temperature of 364 K has been found for 6 nm whereas only
CBH behavior is observed for 52 nm.
DIELECTRIC ANALYSIS
The outcome of frequency on the dielectric constant (E0 )
of CoFe2O4 sintered at 400  C and 800  C is illustrated in
Fig. 7. The dispersion of dielectric constant is found to
decrease at lower frequencies and remains constant at higher
frequencies. It is due to the fact that beyond a certain fre-
quency of ac electric field, the electron exchange cannot
follow the alternating field giving rise to relaxation
mechanism.49–55 The variation of dielectric constant (e0 )
with temperature, for selected frequencies5 (102, 103, 104,
183905-5 Arunkumar et al.
FIG. 7. Variation of dielectric constant (e0 ) with frequencies of CoFe2O4
sintered at 400  C and 800  C.
105 Hz) is depicted in Figs. 8(a) and 8(b). The dielectric con-
stant (E0 ) decreases, reaches to a minimum at 364 K, and fur-
ther increases with temperature indicating metallic to
semiconducting transition for 400  C sintered sample. But
the dielectric constant increases with the temperature contin-
uously from 5.7 to 8.7 (for 1000 Hz), exhibiting normal
behavior of a semiconducting ferrite for 800  C sintered
sample.30 Dielectric constant for 1000 Hz changes from 18.4
to 11.45 and further it increases to 22 for the sample sintered
at 400  C. The variation of dielectric constant with tempera-
ture varies between 20–50 for 6 nm and 8–12 for 52 nm at
low frequency (Fig. 7), and is attributed to a possible reduc-
tion of Fe2þ content at the B-site.15 The decrease of dielec-
tric constant to very small value indicates decrease of Fe2þ
population at the B-site,56 supporting our discussion for the
increased magnetic moment due to cationic inversion and
the system is in the verge of moving towards metallic nature.
The activation energy of the dielectric relaxation process
was calculated from the electrical modulus (M00 versus log
FIG. 8. Temperature dependence of e0 at selected frequencies of the
CoFe2O4 sintered at (a) 400  C and (b) 800  C. (c) Calculation of activation
energy from ln xp(radian) vs 1000/T of CoFe2O4 sintered at 400  C and
800  C.
J. Appl. Phys. 114, 183905 (2013)
(frequency))55 by linearizing the equation, xp ¼ x0 exp
(EP/kBT) as shown in Fig. 8(c). Similarities in the change
of slope, in the activation energy graph for electrical conduc-
tion (ac and dc) and dielectric polarization, further confirm
the phase transition which occurs at the same temperature.
Significant changes in the activation energy (550.7 meV to
485.2 meV) upon size change are found as in the case of ac
conductivity studies.40,47
MAGNETIZATION STUDIES
The M-H curve of CoFe2O4 at room temperature gives a
picture of ferromagnetic behavior of long range ordering as
shown in Fig. 9. Magnetization increases with increase in
sintering temperature.19,37 When the particle size is 6 nm
magnetization is found to be 22 emu/g. But for 52 nm parti-
cle sintered at 800  C magnetization increases to 46 emu/g as
shown in Table I. Compared to the magnetization values
of cobalt ferrite synthesized by various methods listed in
Table III, the increased magnetization for 6 nm particle size
is attributed to single domain nature of superparamagnetic
behavior. It is evident from the increase in coercivity when
particle size decreases (for 6 nm 1444 G and 52 nm
1144 G).19,57
In ferrites, magnetisation is a function of cation distribu-
tion. Normally in an inverse spinel like cobalt ferrite
(CoFe2O4) Fe occupies A and B sites and Co occupies only
B site. L€uders et al.14 investigated the possibilities of maxi-
mum and minimum magnetization as function of cation
inversion. If there is no cation inversion, magnetization will
be minimum, i.e., all Nickel ion will occupy B site and Fe is
equally shared between A and B sites. The other extreme of
100% cation inversion corresponds to an increase in magnet-
ization of 1200 emu/cm3 in which Ni is occupying only A
site. Hence the observed magnetization in our case is a
consequence of cation inversion, for 52 nm. Our values are
comparable to the reported ones tabulated in Table III and
still smaller variations are attributed to variations in synthe-
sis method.
L€uders et al.14 confirm from XRD, EELS, RHEED, and
HRTEM that there is no other source of metallicity, the
observed increase in magnetic moment is attributed to the
metallic nature of the ferrite. Subseqent to the observation,
FIG. 9. M-H curves of cobalt ferrite sintered at 400  C and 800  C.
183905-6 Arunkumar et al. J. Appl. Phys. 114, 183905 (2013)

8
TABLE III. Magnetization value of CoFe2O4 prepared by various synthesis S. J. Stewart, S. J. A. Figueroa, J. M. Ramallo L opez, S. G. Marchetti,
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9
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13
CoFe2O4 8 Solgel 18 emu/g 0 58 S. E. Shirsath, S. S. Jadhav, B. G. Toksha, S. M. Patange, and K. M.
Jadhav, J. Appl. Phys. 110, 013914 (2011).
“ 4 lm Hydrothermal 4000 emu 545 59 14
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16
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17
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19
M. Desai, S. Prasad, N. Venkataramani, I. Samajdar, A. K. Nigam, N.
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20
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CONCLUSION 21
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CoFe2O4 nanoparticles have been synthesized by solgel 22
T. L. Templeton, A. S. Arrott, A. E. Curzon, M. A. Gee, X. Z. Li, Y.
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23
conducting behavior is found at room temperature, which is N. Ponpandian, A. Narayanasamy, C. N. Chinnasamy, N. Sivakumar,
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Superparamagnetic single domain to multi-domain transition 24
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25
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27
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32
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