Materials Letters 61 (2007) 3124 3129

www.elsevier.com/locate/matlet

Sub 5 nm magnetite nanoparticles: Synthesis, microstructure,

and magnetic properties
Jun-Hua Wu a , Seung Pil Ko b , Hong-Ling Liu c , Sangsig Kim d ,
Jae-Seon Ju e , Young Keun Kim b,
a

Research Institute of Engineering and Technology, Korea University, Seoul 136-713, Republic of Korea
Department of Materials Science and Engineering, Korea University, Seoul 136-713, Republic of Korea
c
Institute for Nano Science, Korea University, Seoul 136-713, Republic of Korea
d
Department of Electrical Engineering, Seoul 136-713, Republic of Korea
Cooperative Center for Research Facilities, Sungkyunkwan University, Suwon 440-746, Republic of Korea

Received 3 July 2006; accepted 2 November 2006

Available online 27 November 2006

Abstract
Magnetite particles of 24 nm were synthesized by an economic, biocompatible chemical coprecipitation route, with their size tuned by the
reaction temperature. The microstructure and morphology of the nanoparticles were characterized by X-ray diffraction (XRD) and high resolution
transmission electron microscopy (HRTEM), whereas the magnetic properties were investigated by vibrating sample magnetometry (VSM) and
superconducting quantum interference device (SQUID). It is found that the nanoparticles demonstrate well-defined superparamagnetic behavior as
prepared and after annealing. Distinct lattices were observed which manifest the high crystallinity of such ultrasmall particles and the finite-size
effect was revealed by analyzing the corresponding microstructure and magnetism.
2006 Published by Elsevier B.V.
PACS: 61.46; 81.05.Y; 75.50.V; 75.60
Keywords: Magnetite; Nanoparticle; Coprecipitation; Superparamagnetism

1. Introduction
Magnetic nanoparticles offer exciting opportunities in fundamental study and technological applications, such as in high
density data storage [1], biomedical applications [2,3], color
imaging [4], bioprocessing [5], magnetic refrigeration [6], catalysts [7], ferrofluids [8], among many others. The appeals of
those nanoparticles arise from their reduced dimension with
unique properties different from their bulk counterparts. The
large surface-to-volume ratio leads to unusual coupling and
interaction of the surface atoms sitting a modified local environment. The role of the surface atoms becomes more important as the contributions from surface and volume change
substantially with the decreasing size. Unlike bulk ferromagnetic materials which easily form multiple crystal and magnetic
domains, magnetic nanoparticles can take single crystal and
Corresponding author. Tel.: +82 2 3290 3281; fax: +82 2 928 3584.
E-mail address: ykim97@korea.ac.kr (Y.K. Kim).
0167-577X/$ - see front matter 2006 Published by Elsevier B.V.
doi:10.1016/j.matlet.2006.11.032

magnetic domains as a result of the dimension shrinkage. The

applications, however, are still subject to many limitations, such
as nanoparticle size, size monodispersity, biocompatibility,
magnetization and stability. Practically, an efficient, economic
and scalable synthesis of ultrasmall magnetic particles is highly
desirable for potential applications and fundamental research.
Magnetite (Fe3O4) nanoparticles occupy a singular position in
the field of magnetic materials, owing to its special physiochemical properties. For instance, it exhibits many interesting
phenomena such as charge ordering, mixed valence, and metal
insulator transition known as the Verwey transition [9]. For its
exceptional biocompatibility, magnetite including other forms of
iron oxide nanoparticles has been highlighted for biomedical
applications [10,11], with ultrasmall superparamagnetic iron
oxides mostly interesting for rapid elimination of nanoparticles
and perfusion imaging [12,13]. Fe3O4 nanoparticles can be obtained by several methods, for example, polyol process [14],
precipitation route [15], sonochemical synthesis [16], and microemulsion technique [17]. In this work, we synthesize ultrasmall

J.-H. Wu et al. / Materials Letters 61 (2007) 31243129

3125

size effects revealed in the structural analysis and magnetic

measurements. It is expected that a product from such a clean
process could find applications that require the implementation
of ultrasmall magnetic particles with fine magnetic performance.
2. Experimental

Fig. 1. XRD patterns for the magnetite nanoparticles obtained at 60 C: (a)

before and (b) after annealing. See text for more explanation.

magnetite particles of 24 nm by an economic, biocompatible

coprecipitation route at different reaction temperatures and
report herein the characterization of the morphology, microstructure and magnetic properties of those superparamagnetic
nanoparticles. The ultrasmall magnetic particles show high
crystallinity and well-behaved nanomagnetism, with the finite-

Typically, 30 ml of FeCl3 and FeCl2 aqueous solutions with a

concentration ratio of 2:1 was added dropwise into 200 ml of an
alkali solution under vigorous stirring for 40 min at a controlled
temperature (20 C, 40 C, 60 C or 80 C) to tune the size of
the resultant nanoparticles. Subsequently, the solution was
decanted and centrifuged to obtain dried samples in an oven.
Annealing of the synthesized particles was conducted at 300 C
for 90 min in vacuum or nitrogen. The samples could be well
dispersed in hexane. The microstructure and grain size of the
nanoparticles was acquired by X-ray diffraction (XRD) and
high resolution transmission electron microscopy (HRTEM)
with selected-area electron diffraction (SAED). The magnetic
property of the nanoparticles was analyzed by vibrating sample
magnetometry (VSM) and superconducting quantum interference device (SQUID) at a magnetic field of 100 Oe for both
field-cooling (FC) and zero-field-cooling (ZFC).

Fig. 2. TEM morphology of magnetite nanoparticles obtained at 20 C (a), 40 C (b), 60 C (c) and 80 C (d), respectively.

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J.-H. Wu et al. / Materials Letters 61 (2007) 31243129

3. Results and discussion

Ultrasmall magnetite particles were synthesized by the economic,
non-toxic coprecipitation method at different reaction temperatures.
The crystal structure of the synthesized magnetic nanoparticles was
first analyzed by XRD and HRTEM/SAED. As given in Fig. 1(a) for
the case of the sample prepared at 60 C, the XRD pattern shows a
single-phased cubic inverse spinel structure. In comparison to the
situation of larger particle sizes [1821], the broadening of the peaks in
the present investigation is primarily attributed to the finite-size of the
ultrasmall particle sizes, which is particularly true for the ones before
annealing (Fig. 1(a)). We note that the existence of a defective structure
in the nanosized magnetite is plausible [21]. The finding is further
substantiated by SAED patterns in which diffusive rings prove the
finite dimension of the nanoparticles. According to the Scherrer's
equation [22] in the application to the (311) peak, the grain size of the
nanoparticles as prepared is estimated to be 5 nm (Fig. 1(a)), close to
the HRTEM evaluation of 4 nm (refer to Figs. 2 and 3). After
Fig. 4. Individual dispersion of magnetite nanoparticles obtained at 20 C,
assisted with the addition of oleic acid.

Fig. 3. HRTEM microimages of magnetite nanoparticles obtained at 20 C (a)

and 60 C (b). The distinctive lattices represent respective (311) and (220)
projections of the nanoparticles with high crystallinity.

annealing, the original peaks turn up much sharper and some weak
peaks become stronger (see Fig. 1(b)). Moreover, the appearance of the
new peaks labeled with asterisk may be associated with the possible
forbidden Fe3O4 diffractions and inception of - and -Fe2O3 phases,
owing to the defective structure and oxidation from annealing [21,23].
It is evident that the width of the diffraction peaks reduces significantly,
indicating an increase in the crystallinity and grain size of the annealed
nanoparticles.
Revealed by transmission electron microscopy (TEM) imaging, the
nanoparticles are near spherical in shape, with an average grain size of
24 nm and a narrow grain size distribution. Fig. 2 is the morphologies
of the samples prepared at 20 C, 40 C, 60 C and 80 C, respectively.
It is apparent that the reaction temperature tailors the grain size of the
nanoparticles, from 23 nm at 20 C to 4 nm at 60 C. An appraisal
of the images in Fig. 2 shows that the samples synthesized at 20 C
(Fig. 2(a)) and 80 C (Fig. 2(d)) appear similar and the ones at 40 C
(Fig. 2(b)) and 60 C (Fig. 2(c)) seem alike. We consider the outcome
as a consequence of the competition between nanocrystallite nucleation
and growth commanded by the reaction temperature. The nuclei or the
ratios of the nucleation to growth rates decrease from 20 C to 40
60 C, and then increase again at 80 C. Hence, the grain size changes
alongside the coprecipitating temperature.
As reflected in the XRD patterns of Fig. 1, the nanoparticles
obtained from the coprecipitation process possess high crystallinity,
which is sustained by the HRTEM observation in the way of distinct
lattices from the nanoparticles. As shown in Fig. 3, the (311) and (220)
projections of the lattices are visible for the specimens prepared at
20 C and 60 C, respectively, implying different faceting of the
nanoparticles as a function of the precipitating temperature. It is
straightforward that the physicochemistry and pharmacokinetics of
such nanoparticles is further affected significantly as the lateral dimension of such single nanoparticles is only 35 unit cells, owing to their
large surface area to volume ratio. It is worthy to mention that the
lattice imaging is observable in large-sized magnetite nanoparticles as a
result of high crystallinity due to increasing dimension [18].
Dispersion of nanoparticles is an important issue in the application
of nanoparticles. In our case, the particle dispersion may be improved
by adding a few droplets of oleic acid in the solution of the magnetite
nanoparticles in hexane. Compared to the specimens directly cast from
the samples in hexane (Fig. 2), oleic acid facilitates the physical

J.-H. Wu et al. / Materials Letters 61 (2007) 31243129

separation of the nanoparticles by surface coating and preventing

aggregation of the nanoparticles during the evaporation of the solvent
molecules (Fig. 4) [19].
Subsequently, the magnetic properties of the magnetite nanoparticles were investigated by VSM and a SQUID magnetometer. As presented in Fig. 5, the finite-size effect is demonstrated (as addressed
below) and the results show that the nanoparticles were superparamagnetic at room temperature before and after vacuum annealing.
Panels (a) and (b) of Fig. 5 are hysteresis loops for the samples obtained
at 20 C and at 60 C, respectively. Overall, the two samples give almost
the same order of magnitude of magnetization at the field of 4 T, 19.2
and 24.1 emu/g for the 20 C sample before and after annealing, in
comparison to 16.8 and 20.2 emu/g for the 60 C sample before and after
annealing. As prepared, the 20 C sample is somehow harder to saturate
than the 60 C one; the phenomenon is reversed after annealing where
the former demonstrates a higher susceptibility. Fig. 5(c)(f) presents

3127

both FC and ZFC MT curves obtained from the SQUID measurements

conducted under a magnetic field of 100 Oe. The curves follow a typical
superparamagnetic behavior of magnetic nanoparticles [18]. Before
annealing, the samples have freezing temperatures of 60 K (Fig. 5(c))
for the sample prepared at 20 C and 75 K (Fig. 5(d)) for the sample
prepared at 60 C, respectively, with slightly higher blocking temperatures. The outcome of the difference in the freezing temperatures is
consistent with the change in the grain size, as a reduced grain size
downshifts the temperature. Compared to the polyol process, the
coprecipitation technique produces magnetite of higher freezing temperatures [18]. After annealing, the freezing temperatures shift correspondingly to 170 K (Fig. 5(e)) and 150 K (Fig. 5(f)), whereas the
blocking temperatures increase to 300 K (Fig. 5(e)) and 250 K
(Fig. 5(f)), respectively. The origin of the findings is recognized as a
consequence of increase in the particles sizes due to annealing (see the
detailed analysis below). Furthermore, it is noticeable that there are

Fig. 5. Magnetic measurements for the samples prepared at 20 C (a, c, and e) and at 60 C (b, d, and f). (a, b) MH loops before and after annealing, (c, d) MT loops
before annealing, and (e, f) MT loops after annealing.

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J.-H. Wu et al. / Materials Letters 61 (2007) 31243129

Fig. 6. The fitting of the experimental data to Eq. (4). (a) 20 C samples as prepared, (b) 20 C samples after annealing, (c) 60 C samples as prepared, and (d) 60 C
samples after annealing. Legends: experimental data (circles) and fits (lines).

dips in the field-cooling magnetization at 60 K (Fig. 5(c)) and 75 K

(Fig. 5(d)) for the as-prepared samples and 150 K (Fig. 5(f)) for the
annealed one. The phenomenon could be a manifestation of spin glass
behavior and/or the evidence of a Verwey transition [9], with the first
two much smaller than the bulk value (125 K) which could be due to
the finite-size of the nanoparticles. In contrast, such dips were not
detected in the case of magnetite from polyol process [18].
To elucidate the relation between the particle size and magnetic
properties discussed above, we address the issue of the superparamagnetic magnetization describable by the Langevin function on assemblies of magnetic nanoparticles with freely rotating moments [24,25],
M
1
cotha
MS
a

where
a

lH
kB T


M

MS1

1
cotha1
a1

MS2



1
cotha2
a2

where M1S, M2S, 1 and 2 are the fitting quantities corresponding to

particle size 1 and 2. Fig. 6 shows the fits of the experimental data by

Table 1
The parameters derived from the fitting of Fig. 5(a) and (b) to Eq. (4)

M/MS is the magnetization (M) normalized to the saturation

magnetization (MS), H the applied magnetic field, T the temperature
and kB the Boltzmann constant. For the Langevin-function fit to
experimental data will produce the magnetic moment of the
individual particles, hence it is possible to estimate the dimension of
the nanoparticles. The diameter of a nanoparticle, d, is related to the
corresponding magnetic moment by
k
l MS d 3
6

In our situation, using the bulk value of the saturation magnetization

of MS = 6000 G at 20 C for the magnetic moment of Fe3O4 in the
nanoparticle [26], the size of the magnetic nanoparticles is estimable.
The analysis shows that the data of Fig. 5(a) and (b) can be described
well by a bimodal superposition of Eq. (1), that is, the nanoparticle
systems here have two particle sizes in each sample. So, we use the
equation below to fit the data of Fig. 5(a) and (b),

As prepared

Annealed

R
MS (emu/g)
(Oe)
d (nm)
R
MS (emu/g)
(Oe)
d (nm)

20 C sample

60 C sample

0.99998
22.5 (0.1)
15855.9
(320.8)
2.2
0.99837
14.2 (0.4)
6073.8
(551.3)
3.0

2
5.6 (0.2)
2753.3
(63.2)
3.9
11.7 (0.4)
300.5
(20.0)
8.2

0.99983
13.4 (0.1)
9418.3
(145.2)
2.6
0.99907
17.6 (0.7)
3115.1
(154.8)
3.7

2
6.6 (0.1)
881.6
(13.4)
5.7
5.1 (0.7)
496.6
(72.6)
6.9

J.-H. Wu et al. / Materials Letters 61 (2007) 31243129

Table 2
Comparison of the averaged particle size (d) to the freezing temperature (Tf)

As prepared

Annealed

As prepared

Annealed

by the Grant A050750 of the Korea Health 21 R&D Project,

Ministry of Health & Welfare, and by Grant M1050000010505J0000-10510 from the National Research Laboratory Program of the Korea Science and Engineering Foundation.

2.5
60

5.3
170

3.6
70

4.5
150

References

20 C sample
d (nm)
Tf (K)

60 C sample

Eq. (4) and Table 1 sums up the fitting results, where R is the correlation
coefficient and b kBlT , in addition to the conventions mentioned above
(errors in brackets). From Fig. 6 and Table 1, the fittings agree well with
the experimental data and the nanoparticles are composed of two particle
sizes with different fractions. Both particle sizes increase after annealing.
To correlate with the freezing temperature, the averaged particle
size is calculated in the way of
M d d1 MS d d2
d S 1
MS MS2
1

3129

with d1 and d2 are the particle size 1 and 2. Table 2 compares the
averaged particle size with the freezing temperature. Under the
different experimental conditions, the averaged particle size obtained
from the Brillouin equation, 2.5 and 5.3 nm for the 20 C sample before
and after annealing, compared to 3.6 and 4.5 nm for the 60 C sample
before and after annealing, is close to the ones estimated from the TEM
and XRD analysis. It is obvious that the averaged particle size becomes
bigger after annealing, with more increase of the 20 C sample than the
60 C sample. Moreover, the freezing temperature monotonically increases with the averaged particle size, indicative of the finite-size
effect in determining the freezing temperature.

4. Conclusions
Ultrasmall magnetite particles of 24 nm were successfully
synthesized by an economic, non-toxic aqueous coprecipitation
process, with their size tuned by the precipitating temperature.
From the structural characterization and magnetic measurements, it is shown that the nanoparticles with such small dimension exhibit well-defined superparamagnetic behavior as
prepared and after annealing. Distinct lattices are observed
demonstrating the high crystallinity of such nanoparticles and
the finite-size effect was revealed by analyzing the relevant
microstructure and magnetism. It is expected that a product
from the clean process could be directly employed in applications that require the implementation of ultrasmall-sized
magnetic particles with outstanding magnetic performance.
Acknowledgements
This work was supported by the Korea Research Foundation
Grants KRF-2005-210-D00023 and KRF-2004-005-D00057,

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