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Journal of Magnetism and Magnetic Materials 321 (2009) 37383741

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Journal of Magnetism and Magnetic Materials

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

Magnetic properties of magnetite thin lms close to the Verwey transition

Murtaza Bohra a,b,, Shiva Prasad b,1, N. Venketaramani b, Naresh Kumar c, S.C. Sahoo b, R. Krishnan d
a

Laboratoire de Science et Ge nie des Mate riaux et de Me tallurgie, UMR 7584 CNRS-Nancy. Universite , Ecole des Mines de Nancy, Parc de Saurupt, F-54042 Nancy, France
Indian Institute of Technology Bombay, Mumbai 400076, India
Motilal Nehru National Institute of Technology, Allahabad 211004 India
d
Laboratoire de Magnetisme et dOptique de lUniversite de Versailles, CNRS, 45 Avenue des Etats Unis, 78035 Versailles Cedex, France
b
c

a r t i c l e in f o

a b s t r a c t

Article history:
Received 21 May 2009
Received in revised form
2 July 2009
Available online 16 July 2009

Temperature dependence of the magnetic properties of magnetite thin lm across the Verwey transition
has been investigated. As the temperature is decreased, the magnetization of the lm in a xed eld
showed a sharp decrease close to the Verwey transition temperature (Tv). The MH loops of the lm
have been recorded at various temperatures below and above Tv. It is found that lm does not saturate
at any temperature and saturation becomes more difcult below Tv. While cooling through Tv, the
extrapolated value of magnetization to innite eld (Q), calculated from the numerical t 4pM Q
[1(H*/H)1/2], does not show a drop, but the coefcient indicating difculty in saturation (H*) shows a
sharp rise as does the coercivity.
& 2009 Elsevier B.V. All rights reserved.

Keywords:
Verwey transition
Magnetization
Magnetite

1. Introduction
It is known that magnetite undergoes a structural transition,
known as the Verwey transition, around 120 K [1,2]. This
structural change is accompanied by changes in many of its
physical properties. In a single crystal of magnetite, the most
important change is observed in the resistivity [1,2] which
increases sharply below 120 K, upon cooling. It has also been
reported in single crystals [3,4] that the magnetization at a xed
eld decreases sharply below 120 K, as the temperature is
lowered. However this was a result of increased anisotropy below
the Verwey transition temperature (Tv) caused by a transition to
the lower symmetry phase, because of which the eld was not
enough to saturate the crystal. In addition to this, in magnetite,
one also nds while cooling that the sign of the anisotropy
constant changes from negative to positive, a few degrees above Tv
[5].
Recently, there has been a lot of interest to study thin lms of
magnetite. This is due to its several interesting properties, such as
half metallic nature and high Curie temperature [6]. These make
magnetite a potential spintronic material. Many studies on the
polycrystalline magnetite lms, deposited by different methods
have been reported [79]. However, in these lms, one does not
always see sharp changes in physical properties as in single
 Corresponding author at: Laboratoire de Science et Ge nie des Mate riaux et de
Me tallurgie, UMR 7584 CNRS-Nancy. Universite , Ecole des Mines de Nancy, Parc de
Saurupt, F-54042 Nancy, France.
E-mail address: murtazaphy@gmail.com (M. Bohra).
1
Current address: Director, Indo-French Centre for Promotion of Advanced
Research, 5B, India Habitat Centre, New Delhi 110003.

0304-8853/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2009.07.026

crystals across Tv. This is particularly remarkable for the

magnetization, where sometimes one does not even notice a
clear change close to Tv [7,8]. We have recently reported some
preliminary studies on the deposition of magnetite thin lms
[10,11]. These lms were grown on fused quartz substrate by rf
sputtering [10] and pulsed laser ablation (PLD) [11], with the
substrate kept at room temperature. We had shown in these
papers that while the lm deposited by rf sputtering does not
show a very clear Verwey transition in the resistivity, the same is
clearly seen in the pulsed laser deposited lm, both in the
resistivity and the magnetization.
In this paper, we report a detailed study of the magnetic
properties of magnetite lm, prepared by PLD at heated substrate
of 500 1C, which shows a clearer Verwey transition in comparison
to the room temperature deposited lm reported earlier by us
[11]. Hence this lm was chosen by us for carrying out detailed
studies of MH loops and magnetization, especially close to the
Verwey transition temperature. This study is being reported in
this paper. To the best of our knowledge, such a study has not
been so far reported in polycrystalline magnetite thin lms.

2. Experimental
Magnetite lm with thickness of 800 nm was grown on
amorphous fused quartz substrate by pulsed laser ablation. The
third harmonic (355 nm) of Nd:YAG laser, with 10 Hz repetition
rate and 56 ns pulse width was used to ablate laboratory sintered
a-Fe2O3 (Aldrich-99.99%) target. Deposition was carried out in a

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M. Bohra et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 37383741

vacuum of 1 105 mbar with laser energy density of 2.5 J/cm2 on

to a heated substrate at 500 1C.
X-ray diffraction (XRD) of the lm was taken by a PANalytical
XPert PRO X-ray diffractometer using CuKa radiation. Phase purity
of the lm was also conrmed by micro-Raman spectroscopy,
which is very sensitive to different phases of iron oxides. The
micro-Raman spectra were recorded in the range of
1001000 cm1 with a 6 mW, 514.5 nm Ar+ laser source. Magnetization as a function of eld and temperature was measured with
in plane lm conguration by using a Quantum design PPMS. The
MH loops were taken at various temperatures by applying a
maximum magnetic eld of 10 kOe. Temperature dependence of
magnetization (MT) of the lm was measured by heating the
sample in a xed magnetic eld of 0.5, 5 and 20 kOe. The
diamagnetic contribution from quartz substrate was subtracted
from the MH and MT data by measuring the magnetic
susceptibility of the bare quartz substrate of known mass.
The average grain size of the lm was determined using the
Scherrer formula. This formula relates the nite size line broadening of XRD peaks to the average grain size perpendicular to the
reecting plane. It also uses the value of the Bragg angle of the
corresponding peak. The Bragg angles determined by the XRD
were corrected using high purity silicon as a standard. We used
100% XRD peak (111) to determine the average grain size. For this
purpose the full width half maxima (FWHM) of this peak was
determined and used as the nite size broadening. The size thus
determined was found to be around 70 nm.

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Fig. 2. MT curves at different xed applied magnetic elds.

3. Results
Fig. 1(a) shows X-ray diffraction (XRD) pattern of the lm. All
the observed peaks of the lm can be indexed to magnetite phase
as reported in JCPDS (File no.19-0629). It is clear from Fig. 1(a) that
magnetite lm exhibits preferred ( ) orientation.

Fig. 3. MH loops of magnetite lm at temperatures of 90 and 140 K.

Fig. 1. (a) XRD pattern (b) micro-Raman spectrum of magnetite thin lm.

The micro-Raman spectrum of the lm is shown in Fig. 1(b). In

this gure, four Raman modes located at 664.5, 532.5, 303.3 and
185.2 cm1 are observed, which are consistent with the reported
values of single crystal magnetite [12]. The non-observation of
Raman modes at 227, 297 (a-Fe2O3) and 700 cm1 (g-Fe2O3)
indicates the absence of these phases in our sample [12,13].
Fig. 2 shows the normalized magnetization of the lm, M/
M(300 K), against the temperature in different elds. It can be
seen from this gure that as the temperature is lowered from 125
to 115 K, the magnetization shows sharp decrease. This decrease is
typically 40%, 4% and 0.4% for applied elds of 0.5, 5 and 20 kOe
respectively. This behavior is a signature of the Verwey transition.
Fig. 3 shows MH loops of the lm at 140 and 90 K up to a eld
of 6 kOe for clarity. It is seen from this gure that the coercivity of
the sample at 90 K is signicantly higher than at 140 K. We also
note from the gure that the magnetization does not saturate
even at the highest eld and the slope of MH curve at high eld is
smaller at 140 than at 90 K.
The temperature dependence of coercivity is shown in Fig. 4.
The value of coercivity is slightly smaller at 130 K in comparison to
the room temperature value. However, it increases sharply below
130 K. One can see that at the lowest temperature, the coercivity
of the sample is almost four times its room temperature value.
The sharp increase in the coercivity occurs around the same

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M. Bohra et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 37383741

Fig. 4. Temperature dependence of Hc of the magnetite lm.

temperatures, where the drop was seen in the magnetization in

Fig. 2.

4. Discussion
As was mentioned before, we clearly see that our lms are
( ) oriented. This is in contrast with the lms that were
deposited at room temperature, which showed ( 0) orientation.
However, the room temperature coercivity of the present lm is or
the order of 300 Oe, which is almost sixty percent of what was
observed in the lms deposited by PLD at room temperature and
annealed at 500 1C. The coercivity in the nano-crystalline lms
depends on many factors including the grain sizes. Even though
the crystalline orientation of the lms would play a role, it is
usually masked by these factors. Hence it is not easy to comment
on their absolute values and compare with the room temperature
deposited lms. We, therefore, focus our attention on the
temperature dependence of coercivity only.
Recently there was a report on a detailed study of coercivity in
single crystal magnetite at low temperatures [14]. The coercivity
of the single crystal magnetite was found to be around 1 Oe at
room temperature, which decreased after cooling and reached a
value of less than one tenth of an Oersted near 130 K. The decrease
in the coercivity while lowering temperature was attributed to the
decrease of the magnitude of the crystalline anisotropy constant
K1, which changes sign just above the Verwey temperature. Below
the Verwey temperature, the coercivity showed a much higher
value of the order of 24 Oe. This increase was attributed to the
discontinuous change in the anisotropy and magnetostriction
constants upon the structural change from high symmetric cubic
phase to low symmetric monoclinic magnetite phase. The increase
in the coercivity in a less symmetric phase is seen in other
systems also. In Cuferrite thin lms, for example, an increased
coercivity has been observed in its tetragonal phase in comparison
to the cubic phase [1517]. However, in case of Cuferrite, the
phase does not change simply by changing temperature as in the
present case. The Cuferrite thin lms have to be prepared in
different ways in order to stabilize a particular phase [16,17].
It is clear from Fig. 4 that the coercivity of our thin lm sample
is at least two orders of magnitude higher than that seen in the
magnetite single crystals at all temperatures. This is not surprising. The coercivity in polycrystalline material is generally higher
than in the single crystals due to the presence of grain boundaries.

In our thin lm the coercivity is expected to be even higher than

the bulk polycrystalline materials due to factors like stress and
nano-crystalline grain sizes as was mentioned earlier also [18].
Our results on thin lm also show a small drop in coercivity at
130 K, from its room temperature value, but this is not as
signicant as in a single crystal. Similarly, though there is a rise
in the coercivity in our sample upon cooling through Verwey
transition, the rise is also not so dramatic as in single crystals. This
can be understood, because the crystalline anisotropy is only one
of the many parameters which inuence the coercivity in thin
lms.
The above discussions led us to conclusion that the broad
features of the temperature dependence of coercivity in
nano-crystalline magnetite thin lms can be explained by the
mechanisms similar to the one in single crystals.
Now we discuss our results on the temperature dependence of
the magnetization. We see from Fig. 2 that the drop in
magnetization, while cooling across the Verwey transition, is
quite clear in our lm. We also nd that this drop is smaller for
higher applied elds, as had been observed earlier in the case of
single crystals [3,4]. One would, therefore, like to ask the question
if this drop in magnetization is really due to a change of
the magnetic moment of the ferrite or it is just a manifestation
of the increased anisotropy.
It is known that ferrite thin lms, unlike single crystals, do not
saturate fully even in very high magnetic eld of 70 kOe [9,19].
This phenomenon was observed by Margulies et al. [9] in epitaxial
magnetite lms and was termed anomalous. In a later paper they
explained the non-saturation in terms of the presence of
antiphase boundaries [19]. In nano-crystalline thin lms, where
the grain sizes themselves are only of the order of a few tens of
nanometers, the non-saturation is dominated by many factors like
inhomogeneities present in the thin lms [20]. It is also linked to
the grain size in the sense that lms with larger grain size,
saturate comparatively easily. It is, therefore, believed that the
grain boundary volume could also play a role in leading to
non-saturation [21].
In our lms also, the loops do not saturate at any temperature,
neither above nor below the Verwey temperature. This makes it
difcult to evaluate the intrinsic magnetization of the lm at
different temperatures. We, therefore, adopted the following
strategy.

Fig. 5. High eld data t using the model 4pM Q [1(H*/H)1/2] at temperatures
of 90 and 140 K.

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M. Bohra et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 37383741

3741

We notice from our data that the coercivity and H*, the
coefcient indicating difculty in saturation, behave in similar
way at all the temperatures. This indicates clearly that the factors
affecting coercivity in our thin lms also contribute signicantly
to H*, including crystalline anisotropy. This result is interesting,
because it is not always that H* and the coercivity show similar
temperature dependences. One example is the case of as
deposited Cuferrite lm, where the value of H* is found to
decrease upon lowering the temperature [23], with the coercivity
showing an opposite behavior [24].
Finally, our study shows that the drop in magnetization that is
seen in Fig. 2 is because of increased non-saturation effects caused
by increased anisotropy and non-saturation in the lms.

5. Conclusion
We have investigated temperature dependence of magnetic
properties of magnetite lm close to the Verwey transition. The
MH loops in this lm do not saturate even above the Verwey
temperature. A quantitative analysis of the non-saturation
phenomenon indicates that the temperature dependence of H*,
a measure of the difculty in saturation, has a similar behavior as
the coercivity, both showing a sharp rise while cooling through
the Verwey transition temperature. The extrapolated value of
magnetization to innite eld shows no drop in the saturation
magnetization of the thin lm, while cooling across the transition,
within experimental accuracy.
Fig. 6. Fitted value of H* and Q as a function of temperature.

References
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"
  1=2 #
H
1
4pM Q 1 
H

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