Characterization of iron oxide nanoparticles by

Mössbauer spectroscopy
Saeed Kamali-M, Tore Ericsson and Roger Wäppling,
Department of Physics, Uppsala University, Box 530, SE–751 21 Uppsala, Sweden
Abstract

Small particles of iron oxides, nominally 7 nm and 13 nm in diameter, have been

studied by 57 Fe Mössbauer spectroscopy in the temperature range 4 K to room tem-
perature. The Mössbauer spectra show, at high temperature, relaxational behaviour
in agreement with the superparamagnetism expected. At low temperature the spin
motion becomes slower and, finally, blocked. There are also indications that the
material is non-stoichiometric.

Key words: Nanoparticles, Iron oxides, Mössbauer spectroscopy, Magnetic

hyperfine field, Centroid shift, Superparamagnetism
PACS: 75.75.+a, 76.80.+y

1 Introduction of nanometers and less, each grain

Small particles, thin films etc. have
been subject to intensive research
during the last decades as many of
the physical properties are different
compared to bulk characteristics.
The increased area to volume ratio
in small particles is of highest impor-
tance in surface-sensitive catalysts.
In recording media like magnetic
tapes a suitable choice of coercivity
and remanence is the basis for the
use of small magnetic particles, as
well as for the increased information
density. In bulk materials domain
walls are created minimizing the
magnetic stray energy. However, in
small particles with diameters of tens
Email address:
saeed.kamali@fysik.uu.se (Saeed
Kamali-M).
URL:
http://material.fysik.uu.se
(Saeed Kamali-M).
may be a magnetic single domain. In
these cases the magnetic anisotropy
energy will be proportional to the
volume of the grain, which may give
paramagnetic (PM) behaviour, even
if the material is in the magnetically
ordered state, so called superpara-
magnetism (SPM). Then the transi-
tion from PM- to e.g. ferro- (FM) or
ferrimagnetic (FiM) behaviour will
depend on particle size, temperature
and also the time scale used in the
chosen instrument for the investiga-
tion.
FM or FiM nanoparticles of iron
oxides are also candidates for can-
cer treatments as a way to promote
cell necroses using controlled local
heating of tissue, leading to hyper-
thermia [1]. Magnetic nanoparticles
coated with a lipid bilayer, so called
magnetoliposomes (ML), are used
due to their biocompatibility [2,3].

Preprint submitted to Elsevier Science 28 October 2005

The temperature of the ML is then
raised by applying a AC magnetic
field. To obtained maximum heat
transfer for lowest possible field-
strength and ML concentration the
ML size, as well as core-material
and AC frequency has to be opti-
mized. Here we report on the use
of Mössbauer spectroscopy for char-
acterizing such nanoparticles as a
complement to other techniques.
2 Experimental
Two samples, prepared in the de-
partment of material science at Uni-
versity of Washington, Seatle were
used in the investigation. Iron pen-
tacarbonyl was injected into a hot
solution containing oleic acid and
the nucleation size depended on the
molar ratio of oleic acid to iron pen-
tacarbonyl. After chemical treat-
ments, small particles of magnetite
were achieved and we studied two
fractions, being nominally of 7 nm
and 13 nm of grain size characterized
by transmission electron microscopy
(TEM) and X-ray diffraction (XRD)
studies. For further details see [4].
The Mössbauer absorbers were pro-
duced by mixing the sample material
with boron nitride powder and then
pressed to a self supported disc. The
transmission 57 Fe Mössbauer spec-
trometer used was of conventional
type, working in constant acceler-
ation mode. The movement of the
radioactive CoRh source, held at
room temperature, was controlled by
a locally constructed computerized
interface. The absorber was kept at
the desired temperatures using a He
flow cryostat. The recorded spectra
were analyzed using the program
”Recoil”, developed by Lagarec and
2
Rancourt [5]. The center shift (CS) is
given relative metallic iron at room
temperature. As the amount of stud-
ied material was quite low and the
small particles were roughly spher-
ical, as seen in the TEM study [4],
we assumed no thickness or texture
effects when analysing the spectra.
3 Result
In Fig.1, some representative Mössbauer
spectra are shown. The particle size
is influencing the spectra in an ob-
vious way: the 7 nm particles are
showing fast relaxation at room tem-
perature and slow relaxation at low
temperatures, the 13 nm particles
are showing mainly intermediate to
slow relaxation in the whole tem-
perature range studied. However, as
relaxational effects are seen in a very
broad temperature interval for both
samples, they show features indicat-
ing a considerable spread in particle
sizes which can be estimated by using
the Néel-Brown formula concerning
the superparamagnetic relaxation
time [6,7],
KV
τ = τ0 [ ] (1)
kT
Here T is temperature, k is the Boltz-
mann constant, K is the magnetic
anisotropy energy constant, V is the
volume of the single domain and τ0
is in the order of 10−12 − 10−9 s. The
estimated spread in sizes is ±2 as
compared to [8] and in fair agree-
ment with [4]. The room tempera-
ture spectrum of the 7 nm sample,
Fig.1, also shows a dominant doublet
having a CS equal to 0.31 mm/s and
a quadrupole splitting (QS) equal to
0.84 mm/s. Obviously, this doublet
emanates from ferric iron in an non-
spherical local surrounding, may be
coming from the rim of the iron-
oxide core. The broad wings in the
spectrum is typical for SPM particles
close to the blocking temperature
TB , which is defined as the transition
temperature from fast to slow relax-
ation. They are fitted using a spread
in hyperfine fields from 8 to 25 T
having CS in the range 0.44 mm/s
to 0.69 mm/s. As the CS values are
higher than normal for ferric iron in
oxides, they indicate an iron valence
state between +3 and +2, but closer
to the former.
The low temperature spectra are
shown with fittings in Fig.2. The
broad data profile needs at least two
sextets for acceptable fits, thus ex-
cluding iron-oxides like hematite or
goethite, as those are only having
iron in one crystallographic site. On
the whole, however, the spectra are
typical for magnetite below the Ver-
wey temperature.
The obtained Mössbauer parameters
for the two sextets are both typical
for ferric iron in high spin configura-
tion. However, the hyperfine fields,
Bhf for the 7 nm sample are about
1 T lower compared to the respec-
tive fields in the 13 nm sample. A
possible cause could be collective ex-
citations in small magnetic domains
which will reduce the observed hy-
perfine fields, Bobs , as compared to
the bulk value, Bhf0 [9],
kT
Bobs ≈ Bhf0 [1 − ] (2)
2KV
In Fig.3 is shown Mössbauer spec-
tra of the 13 nm sample recorded
at 170 K and magnetite at room
temperature. In stoichiometric mag-
netite, Fe3 O4 , the Verwey transition
takes place at 119 K. Above this
temperature the Mössbauer spec-
trum profile shows a clear separation
3
into tetrahedral- (A) and octahedral-
(B) sites having Bobs (A) ≈ 51 T
and Bobs (B)≈ 48 T ([10]) at 160 K.
However for non-stoichiometric mag-
netite, with γ-Fe2 O3 (maghemite)
as the end composition, there is no
electron hopping and the ferric iron
at B-sites has Bobs ≈51 T at 160 K,
thus roughly the same value as for
Fe3+ (A) [10]. In our sample there
is neither a clear separation into A-
and B-sites nor the clear difference in
CS for B- and A-sites of ≈0.4 mm/s
measured in Fe3 O4 . Thus we con-
clude that the MLs studied here do
have the magnetite structure but be-
ing non-stoichiometric as a result of
the chemical manufacturing process.
By using the CS values of differ-
ent compounds and comparing them
with the average CS value of these
samples, one arrives at a composi-
tion of approximately 32% γ − Fe2 O3
and 68% Fe3 O4 .
References
[1] R. Hergt, W. Andrä, C.G. d’Ambly,
et al., IEEE Trans. Magn. 34 (1998)
3745.
[2] M. De Cuyper, P. Müller,
H. Lueken, M. Hodenius, L. Phys.:
Condens. Mat. 15 (2003) S1425.
[3] M. De Cuyper, M. Joniau, Eur.
Biophys. J. 15 (1988) 311.
[4] M. Gonzales, K.M. Krishnan, J.
Magn. Magn. Mater 293 (2005)
265.
[5] K. Lagarec and D.C. Rancourt,
Recoil, Mössbauer spectral analysis
software for Windows, version 1.0,
1998.
[6] L. Néel, Ann. Geophys. 5 (1949) 99.
[7] W.T. Brown Jr., Phys. Rev., 130
(1963) 1677.
[8] F. Bødker, M.F. Hansen,
C.B. Koch, K. Lefmann and
S. Mørup, Phys. Rev. B 61 (2000)
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[9] S. Mørup, J. Magn. Magn. Mater

Intensity (Arbitrary unit)

(13nm, 6K)

37 (1983) 39.
[10] A.R. Muxworthy and
E. McClelland, Geophys. J. Int. 140
(2000) 101.
(7nm, 6K)

-10 -5 0 5 10
Velocity (mm/s)
(7nm,293K)

Fig. 2. The Mössbauer spectra at 6 K

for both particle sizes.
Intensity (Arbitrary units)

(7nm,200K)

(7nm,78K)

(7nm,60K)
Intensity (Arbitrary units)

o
Magnetite, 290 C

(7nm,6K)

-10 -5 0 5 10
Velocity (mm/s)

(13nm,170K)

-10 -5 0 5 10
Velocity (mm/s)
(13nm,170K)

Fig. 3. The Mössbauer spectra for

(13nm,100K)
13 nm particles and magnetite mea-
Intensity(Arbitrary units)

sured above the Verwey temperature.

(13nm,78K)

(13nm,60K)
Table 1
The magnetic hyperfine field B and
Centroid Shift (CS) of the different
(13nm,6K) components of the both samples. Esti-
-10 -5 0 5 10
mated errors in B are 0.2 T and in CS,
Velocity (mm/s)
0.01 mm/s.
Fig. 1. The Mössbauer spectra at differ-
ent temperatures for 7 nm particles (up- Samples CS1 Bhf1 CS2 Bhf2
per) and 13 nm particles (lower) parts. (mm/s) (T) (mm/s) (T)
7 nm 0.44 50.1 0.48 52.4
13 nm 0.41 51.0 0.48 52.9