Synthesis and Investigation of

Electrodeposited Half-Metallic Fe3O4

Thin Films and Nanowires

Journal of Superconductivity
and Novel Magnetism
Incorporating Novel Magnetism

ISSN 1557-1939
Volume 24
Combined 1-2

J Supercond Nov Magn (2010)

24:845-849
DOI 10.1007/s10948-010-1027-
y

1 23
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 Author's personal copy
J Supercond Nov Magn (2011) 24: 845–849
DOI 10.1007/s10948-010-1027-y
O R I G I N A L PA P E R
Synthesis and Investigation of Electrodeposited Half-Metallic
Fe3 O4 Thin Films and Nanowires
Mamraj Singh · Sujeet Chaudhary ·
Subhash C. Kashyap · D.K. Pandya
Received: 14 September 2010 / Accepted: 17 September 2010 / Published online: 8 October 2010
© Springer Science+Business Media, LLC 2010
Abstract Thin films and nanowires of Fe3 O4 have poten-
tiostatically been electrodeposited on ITO coated glass and
employing templates in a conventional three-electrode cell
using two different baths. Appropriate potential windows,
suitable for films and nanowires, were estimated from cyclic
voltametry. Structural property of Fe3 O4 films was studied
by X-ray diffraction. A large (−3.35%, at 2.3 kOe) lon-
gitudinal magnetoresistance (MR) was observed at room
temperature, and the shape of MR curves showed a re-
duced hysteresis loop for Fe3 O4 films with low coercivity.
Room-temperature magnetic properties of Fe3 O4 films were
studied by vibrating sample magnetometer (VSM). Surface
morphology of nanowires was studied by scanning elec-
tron microscope (SEM). The nonlinear I –V characteristic
of nanowires was observed at room temperature. An attempt
has been made to understand the conduction mechanism.
Keywords Electrodeposition · Fe3 O4 · Half metallic
systems · Thin films · Magnetoresistance
1 Introduction
Magnetite (Fe3 O4 ) is a magnetic iron oxide that has a cubic
inverse spinel structure [1]. The band structure calculations
of the Fe3 O4 indicate a half-metallic nature with a gap in the
density of states of majority carriers [2]. Half-metallic mate-
rials such as CrO2 , La0.7 Sr0.3 MnO3 (LSMO) and Fe3 O4 are
highly attractive for spintronics applications (TMR, GMR
M. Singh · S. Chaudhary () · S.C. Kashyap · D.K. Pandya
Thin Film Laboratory, Department of Physics, Indian Institute of
Technology Delhi, New Delhi 110016, India
e-mail: sujeetc@physics.iitd.ernet.in
and spin transistors, etc.) because of their high spin po-
larization [3]. Among these materials, magnetite is supe-
rior to others owing to its high Curie temperature (858 K)
and high spin polarization (theoretically ∼100%) at room
temperature [4]. Ideally 1D structure of Fe3 O4 nanowires
with obvious perpendicular magneto-anisotropy may be a
good candidate for high-density magnetic recording me-
dia [5]. Various techniques are employed for the fabrica-
tion of nanowires [6–8]. A straightforward approach is the
template technique in which the nanowires are grown within
pores of a template generally of a porous alumina or a poly-
mer [9]. On the other hand, the Magnetite films have been
deposited onto polycrystalline and single-crystal substrates
using several vacuum based technique including pulsed laser
ablation [10–13], molecular beam epitaxy [14, 15], sput-
tering [16–18], and a simple technique of electrodeposi-
tion [19–21]. Coey et al. investigated the magnetoresistance
(MR) of Fe3 O4 in the form of polycrystalline thin films,
powder compacts, and single crystals at room temperature
(RT), and reported a maximum value of 1.6% at 5 kOe [22].
Kothari et al. observed 6.5% (at 90 kOe) MR and at room
temperature [20].
In this paper, we report our studies on the role of
grain boundaries on magnetotransport properties of elec-
trodeposited Fe3 O4 thin films. A room-temperature non-
saturating MR value of 3.34% was estimated at relatively
small field of 2.3 kOe. The magnetic hysteresis of thin
films exhibited shape anisotropy. In addition, we have also
grown Fe3 O4 nanowires by electrodeposition and studied
their electrical transport.
2 Experimental
The electrodeposition was performed using CH-Electro-
chemical Analyzer (Model-1100A) in a three-electrode cell.
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846 J Supercond Nov Magn (2011) 24: 845–849

The cell consisted of a standard calomel reference electrode

(Hg/HgCl2 /KCl), and a counter electrode of Pt (area of
2 cm × 1.5 cm). The potential windows for electrodeposit-
ing thin films on a substrate and nanowires in a template
were estimated using cyclic voltametry. The Fe3 O4 films
and nanowires were electrodeposited in two different baths.
The details of bath composition are given below.
The magnetite films were electrodeposited on to ITO
coated glass at two temperatures for 1000 s using an alkaline
aqueous solution (pH = 12.33) of Fe2 (SO4 )3 complexed
with triethanolamine (TEA) [20]. The concentration of the
deposition bath was 0.18 M Fe (III), 0.1 M TEA, and 2 M
NaOH [21]. A potential difference of −1.16 V was applied
to the working electrode with respect to standard calomel Fig. 1 Glancing angle X-ray diffraction (GAXRD) patterns of elec-
trodeposited Fe3 O4 film samples, S-1 (55 ◦ C, ITO) and S-2 (75 ◦ C,
electrode (SCE). Finally, we have two types of electrode-
ITO)
posited Fe3 O4 film samples (a) S-1 and (b) S-2 electrode-
posited at 55 and 75 ◦ C, respectively. In another bath, an
aqueous solution containing 3 g/L of (NH4 )2 SO4 ·FeSO4 ·
6H2 O, 3 g/L of KNO3 , few drops per liter of HCl and
N2 H4 ·H2 O with a pH of 5.58 were used to synthesize Fe3 O4
nanowires [23]. A voltage of −0.86 V was applied to the
conducting surface of the working electrode Ag coated poly-
carbonate templates (PCT), having an average pore size of
50 nm and pore length of 6 μm and the electrodeposition
was carried out at 80 ◦ C for 1400 s. The process has been
carried out by bubbling Ar gas inside the electrolyte to avoid
unwanted reaction.
The synthesized Fe3 O4 thin films were characterized by
Philips X-ray diffractometer (Model X’Pert PRO) at a scan-
ning rate of 0.05◦ /s with 2θ ranging from 25 to 70◦ using Cu
Kα radiation (λ = 1.5406 Å). The magnetoresistive trans-
port measurements were made by a dc two-probe method us-
ing programmable current source (Keithley 224) and a nano-
voltmeter (Keithley 181). The study of room-temperature
magnetic properties was carried out by a vibrating sample Fig. 2 The scanning electron microscope images of electrodeposited
Fe3 O4 nanowires
magnetometer (VSM-EG&G Princeton Applied Research,
Model-155). The scanning electron microscope (SEM) im-
ages of the nanowires were obtained by a ZEISS EVO-50 79-0418), and thus establish the formation of Fe3 O4 cubic
scanning electron microscope. We have also performed elec- phase in these electrodeposited thin films. In addition, a peak
trical transport measurement on nanowires, and a current at 2θ = 30.6◦ belongs to γ -Fe2 O3 . The mean crystallite size
vs. voltage (I –V ) curve was recorded by applying a slowly for samples S-1 and S-2, estimated by using the Scherrer
varying potential difference across the sample. formula [24], is 23 and 28 nm, respectively. The increase in
grain size is understandable as the temperature of deposi-
tion bath is increased from 55 to 75 ◦ C. The scanning elec-
3 Results and Discussion tron microscope (SEM) image of the nanowires (Fig. 2) was
recorded after dissolving the template in CH2 Cl2 . The aver-
3.1 Structure and Morphology age diameter of the nanowires is about 100 nm.

The glancing angle X-ray diffraction (GAXRD) spectra of
Fe3 O4 thin films (S-1 and S-2), recorded at a glancing angle
of 0.5◦ , are shown in Fig. 1. These spectra and calculated
value of the lattice parameter of 8.395 Å are in good agree-
ment with standard data of the Fe3 O4 cubic phase (JCPDS
3.2 Electrical Transport (I –V ) Properties
In order to investigate the electrical transport behavior of
electrodeposited Fe3 O4 nanowires at room temperature,
a two-probe current vs. voltage (I –V ) measurement was
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J Supercond Nov Magn (2011) 24: 845–849
Fig. 3 Room-temperature current–voltage (I –V ) plot of electrode-
posited Fe3 O4 nanowires
Fig. 4 Conductance (G) vs. applied voltage (V ) curve for Fe3 O4
nanowires at room temperature, and the solid line is the best-fit curve
made. The observed nonlinear I –V characteristic (Fig. 3)
may be attributed either to the tunneling of the carriers
through the insulating γ -Fe2 O3 barriers at the grain bound-
aries or to inelastic hopping via localized states [22, 25, 26].
The dynamic conductance (G = dI /dV ) of the nano-
wires varies with applied potential difference V as
G(V ) = G0 + kV α (1)
where G0 is the conductance of the nanowires at zero volt-
age, k and α are constants. It is reported that a theoretical
value of α = 1.33 is predicted for inelastic hopping via two
localized states [26] and a value of α = 2 is predicted for
direct tunneling [27]. Further, the value of α = 2 is pre-
dicted for a spin-flip scattering process [28] also. Using the
I –V data, we have plotted dynamic conductance (G) of the
nanowires as a function of applied voltage (Fig. 4). In our
847
Fig. 5 Room-temperature hysteresis loop measured with the magnetic
field (H ) applied parallel and perpendicular to the film sample (S-1)
surface at room temperature. Insert shows the curve near the origin in
expanded scale
case, the best fit satisfies (1) with G0 = 1 μ−1 , and
G
= 1 + 1.75V 1.49 . (2)
G0
The estimated value of α = 1.49 lies between 1.33 and 2.
It may, therefore, be inferred that the inelastic hopping
via localized states is more dominant than direct tunnel-
ing or spin-flip scattering process. This could be due to
defect structure (oxygen defects or cation disorder) of the
nanowires, which gives rise to localized states.
3.3 Room-Temperature Magnetic Properties
Figures 5 and 6 show hysteresis (M-H) loops of the elec-
trodeposited Fe3 O4 film samples S-1 and S-2, respectively
recorded at RT. In each case, the measurement was per-
formed with the magnetic field in both configurations, par-
allel and perpendicular to the film surface. It is evident from
the inset in these figures that the samples S-1 and S-2 have
in-plane coercivity of 78 and 93 Oe, whereas perpendicu-
lar coercivity values are 84 and 126 Oe, respectively. On
further investigation, we have observed that the sample S-2
shows a clear effect of shape anisotropy, as evidenced by
different M-H behavior recorded in the in-plane and perpen-
dicular magnetization as compared to S-1. It is reported that
the bulk magnetite has a relatively weak magnetocrystalline
anisotropy K1 = −1.1 × 104 J/m3 at room temperature.
This value is considerably lower than the experimentally es-
timated values of shape anisotropy (KS = μ0 (M S )2 /2) =
1.55 × 104 and 8.36 × 104 J/m3 at room temperature for
samples S-1 and S-2, respectively [29]. The observed value
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848
Fig. 6 Room-temperature hysteresis loop measured with the magnetic
field (H ) applied parallel and perpendicular to the film sample (S-2)
surface at room temperature. Insert shows the curve near the origin in
expanded scale
of saturation magnetization for S-1 and S-2 films was found
to be 30 and 70 emu/g, respectively. The saturation mag-
netization of the S-1 is relatively small as compared to S-2,
because of γ -Fe2 O3 phase (72 emu/g) and smaller grain
size (exchange length of Fe3 O4 , Λex = 27 nm). It is also
likely that the smaller saturation magnetization compared to
the expected value of 92 emu/g is due to the nonlinear spin
structure, possibly originating from the pinning of the spins
near the grain surfaces.
3.4 Magnetoresistive Transport Properties
It is known that, in a granular magnetic system, the resis-
tance at room temperature is composed of two parts. First
is the field-independent part due to the usual contributions
from electronic scattering due to phonons, defects and impu-
rities. Second part is field dependent, and is responsible for
the MR because of the dependence of magnetization (M)
of the grains on the external magnetic field. The external
magnetic field tends to rotate the magnetization direction of
the grains and the resulting rotation accordingly reduces the
resistance. The MR hysteresis loop of a granular magnetic
system is essentially a signature of rotation of the magneti-
zation directions toward applied field.
According to Xiao et al. in a granular system, the
(M/MS )2 is proportional to cos θ 2 , where θ is the an-
gle between the magnetization direction (inside a grain) and
the applied field, and cos θ 2 is averaged over many ferro-
magnetic grains [30, 31]. This is because in a system of ran-
domly aligned FM domains, the electrical resistance, aris-
ing due to scattering at the domain walls, is proportional to
J Supercond Nov Magn (2011) 24: 845–849
Fig. 7 Longitudinal magnetoresistance of electrodeposited Fe3 O4
film sample S-1 (55 ◦ C, ITO) at room temperature and the fitted curve,
MR = −3.8(M/MS )2 , using magnetization data of sample S-1
cos Φij , where Φij is the relative angle between the mag-
netization directions of grain i and grain j , and for non-
interacting ferromagnetic domains, cos θ 2 = cos Φij [30].
This yields
 2
M
MR ∝ cos θ  ∝ cos Φij  ∝
2
.
MS
Therefore, for grain boundary scattering dominated MR
behavior, the MR should possess a quadratic dependence on
M in the granular electrodeposited Fe3 O4 samples S-1 and
S-2, provided the ferromagnetic grains are non-interacting.
For the measurement of the (longitudinal) magnetore-
sistance, a magnetic field was applied (in plane) paral-
lel to the dc current flowing in a thin film. The magne-
toresistance was calculated using the equation MR(%) =
[(RH ∼0 − RH )/RH −max ] × 100, where RH ∼0 is electrical
resistance at coercivity, HC (see Figs. 7 and 8). It may be
noted from Figs. 7 and 8 that MR values for samples S-1
and S-2 are 3.07% and 3.35% at 2.3 kOe, respectively. The
hysteresis in the MR plot reveals a coercive field of 105
and 130 Oe for samples S-1 and S-2, respectively. The MR
curves show that the maximum resistance occurs at the coer-
cive field. These observations suggest that the grain bound-
aries play an important role in electrical transport behavior
in presence of applied magnetic field. For further analysis
of the observed shape of the MR curves, the magnetoresis-
tance values were compared with the square of the normal-
ized magnetization (M/MS ) estimated from the M-H loop
for both the samples (S-1 and S-2). The observed MR vs. H
plots, and the plot of the equation
 2
M(H )
MR(H ) = −C
MS
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J Supercond Nov Magn (2011) 24: 845–849
Fig. 8 Longitudinal magnetoresistance of electrodeposited Fe3 O4
film sample S-2 (75 ◦ C, ITO) at room temperature and the fitted curve,
MR = −2.8(M/MS )2 , using magnetization data of sample S-2
with scaling parameter C = 3.8 (sample S-1) and C = 2.8
(sample S-2) are shown in Figs. 7 and 8. As can be seen,
the scaling is neither very good nor can we say that it is ab-
sent altogether. It is, therefore, suggested that conductance
character in these Fe3 O4 films is a mixed case. Apart from
the dominant spin-polarized tunneling across the randomly
oriented grains [30], the transport is also governed in part
by spin disorder scattering at the grain boundaries [31]. It
may be noted that a similar conclusion was drawn based on
nonlinear I –V studies of these films.
4 Conclusions
We have studied the magnetite films and nanowires syn-
thesized by an electrochemical deposition technique. The
Fe3 O4 films have the characteristics of a granular system,
such as relatively small saturation field (1.5 kOe) and large
magnetoresistance (MR = 3.35% at 2.3 kOe) at 300 K. The
observed MR shape, which is closely correlated with the
magnetization [MR(%) = −C(M/MS )2 ] of thin films, fur-
ther confirms that the thin films behave like a non-interacting
granular system. These films are suitable for the develop-
ment of magnetic sensors. The temperature of electrode-
position has played a role in inducing shape anisotropy in
Fe3 O4 films. It is proposed that the conduction mechanism
in Fe3 O4 nanowires is predominantly governed by spin-
polarized tunneling across the Fe3 O4 grains with finite con-
tributions arising due to carrier hopping via localized states.
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