PHYSICAL REVIEW B 70, 092409 (2004)

Surface spin glass and exchange bias in Fe3O4 nanoparticles compacted under high pressure
H. Wang,1 T. Zhu,1,* K. Zhao,2 W. N. Wang,1 C. S. Wang,1 Y. J. Wang,1 and W. S. Zhan1
1State
Key Laboratory of Magnetism, Institute of Physics and Center for Condensed Matter Physics, Chinese Academy of Sciences,
P. O. Box 603, Beijing 100080, People’s Republic of China
2Magnetoelectronics Lab, School of Physics Science and Information Technology, Liaocheng University, Liaocheng 252059, People’s

Republic of China
(Received 4 February 2004; published 29 September 2004)

We have demonstrated a low temperature surface spin-glass layer in the Fe3O4 high-pressed nanocompacts.
The related core-shell magnetic structure arises during the compaction, which is evident by the field depen-
dence of the freezing temperature following the de Almeida–Thouless relationship and obvious exchange bias
effect. Moreover, we have also found a critical cooling field, above which both the surface spin-glass behavior
and the exchange bias effect abruptly disappeared.

DOI: 10.1103/PhysRevB.70.092409 PACS number(s): 75.50.Tt, 75.75.⫹a, 75.50.Gg

I. INTRODUCTION
Magnetic nanoparticles have been a subject of intense re-
search in the past decade because of their unique
properties.1–4 One of the important issues in magnetic nano-
particles is the surface spin configuration. It has been already
found that the saturation magnetization M S of magnetic
nanoparticles is reduced due to the different spin
configuration,5,6 or a random canting of the particle surface
spins is caused by competing antiferromagnetic exchange in-
teractions at the surface.7 Polarized neutron scattering in
ball-milled CoFe2O4 particles2 or Mössbauer8 experiments in
NiFe2O4 nanoparticles have also been consistent with the
model of a ferrimagnetic (FM) core of aligned spins sur-
rounded by a shell with spin disordered. The simulation of
the magnetic behavior based on the core-shell model has
been done and very well agreed with the experiments.9 On
the other hand, the phenomena of a surface spin glass are
strongly dependent on the particle size and will completely
disappear when the mean particle size is beyond a critical
value, for example, 20 nm for ␥-Fe2O3.4
Magnetic nanoparticles can be fabricated by a lot of tech-
niques, such as mechanical ball milling,2,3 chemical
precipitation,4,7 and the sol-gel process.10,11 In this paper, we
show evidence of the existence of the surface spin-glass be-
haviors in the Fe3O4 nanoparticles compacted under high
pressure, whereas such behaviors cannot be observed in un-
compacted samples due to their large grain size above the
critical size. This demonstrated that the core-shell structure is
forming in the magnetic nanoparticles by using the high-
pressure compaction. The increase of the freezing tempera-
ture 共TF兲 of the surface spin glass with compaction pressure
has been observed. Moreover, the surface spin glass in Fe3O4
high-pressed nanocompacts will vanish under a high cooling
field, accompanied by the disappearance of the exchange
bias effect.
droxide 共NaOH兲 were used as the starting reagents. The sto-
ichimetric ferrous sulfate and sodium hydroxide aqueous so-
lutions were mixed slowly under magnetic stirring to form
the pale green Fe共OH兲2 rust. Then the oxidation reaction of
Fe共OH兲2 took place by heating while flowing air. Finally,
after oxidation for 1 – 3 h, the magnetite particles formed. By
controlling the temperature and the time of oxidation reac-
tion, we can obtain pure magnetite nanoparticles. The aver-
age particle size of the sample in this paper was about 20 nm
estimated by x-ray diffraction (XRD) and scanning electron
microscopy (SEM) as shown in Fig. 1. Then the Fe3O4 nano-
compacts were made by a quasihydrostatic pressure method
at room temperature under pressures ranging from 1 to
5 GPa. To stabilize the volume change for each sample, the
pressure was applied for 45 min. No obvious shape change
and preferential ordering can be observed after compaction
by using XRD and SEM. Magnetic properties of the samples
have been measured using a commercial superconducting
quantum interference device (SQUID, MPMS-7) in the tem-
perature range from 5 to 300 K and in applied magnetic
fields up to 50 kOe.
III. RESULTS AND DISCUSSION
Figure 2 shows the temperature dependence of magneti-
zation in the zero-field-cooled (ZFC) and field-cooled (FC)

II. EXPERIMENTAL PROCEDURES

Ultrafine Fe3O4 powder was prepared by a wet chemical FIG. 1. The SEM image of the Fe3O4 nanoparticles showing the
method.12 Ferrous sulfate 共FeSO4 · 7H2O兲 and sodium hy- average of particle size as about 20 nm.

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BRIEF REPORTS PHYSICAL REVIEW B 70, 092409 (2004)

FIG. 2. Temperature dependence of low-field ZFC (solid
circles) and FC (open circles) magnetization of the Fe3O4 nanopar-
ticles compacted under 5 GPa. Inset: the low-field FC M-T
curves for 5-GPa (open circles) and uncompacted (solid squares)
samples.
FIG. 3. Field dependence of the spin-glass transition tempera-
ture showing the AT line. TF is obtained by extrapolating the AT line
back to H = 0. The critical cooling field Hcri is defined by the ex-
trapolation of the AT line forward to T = 0. Inset: Compaction pres-
sure P dependence of TF measured under H = 500 Oe.

processes with an applied low field of 500 Oe for Fe3O4 can disappear when H 艌 Hcri. The disappearance of the sur-
nanoparticles compacted under 5 GPa (Fe3O4 5 − GPa nano- face spin-glass in magnetic nanosized oxides has also been
compact). The ZFC curve exhibits a typical blocking process found in Fig. 3 of Ref. 4. The Hcri of about 120 kOe can be
for the superparamagnetic behavior with the blocking tem- estimated for ␥-Fe2O3, which is far beyond the range of
perature at TB ⬇ 100 K. Moreover, the FC curve reveals a common magnetic measurement.
sudden increase in magnetization below about 41 K. This Accompanied with that, the AT line suggests spin disorder
sudden increase of magnetization is much clearer in a careful limited at the surface, and the core-shell structure can also be
measurement of the FC branch, although such surface spin- consistent with the hysteresis loop shift. Figure 4 shows the
glass transitions have not been observed in unpressed typical field-cooled magnetic hysteresis loops of the uncom-
samples due to their particle size above the critical value pacted Fe3O4 nanoparticles and the samples compacted un-
(the inset of Fig. 2). A similar surface effect can also been der 2 and 5 GPa. Here, we define the left 共HC1兲 and right
seen in nanosized ␥-Fe2O34 or perovskite manganites,10,11 coercivity 共HC2兲 as the transition field in the descending and
related to the onset of the freezing process of the surface ascending branch of the loop, respectively, and then the ex-
spin-glass (or spin disordered) layer. In other words, the change bias field HEB as 共HC1 + HC2兲 / 2.15 The inset shows
moments in the surface layer freeze below the spin-glass-like the compaction pressure 共P兲 dependence of HC1 and HC2.
transition temperature and align with the core moments in
the direction of external field in the FC process. Hence, a
core-shell structure can be proposed in the Fe3O4 high-
pressed nanocompacts, and further evidence is given by the
de Almeida–Thouless (AT) relationship, which will be dis-
cussed as follows.
The linear relationship of TF (typical for the Fe3O4
5-GPa nanocompact) versus H2/3 is shown in Fig. 3, corre-
sponding to the so-called AT line given by13,14
HAT共T兲/⌬J ⬀ 共1 − T/TF兲3/2 . 共1兲
Similar to nanosized ␥-Fe2O3 the H dependence ex-
4, 2/3

hibits the existence of a surface spin-glass layer in the nano-

sized magnetic oxides. If spin disorder exists in the whole
volume of the particle, TF should follow the H1/2
dependence.13 Also from Fig. 3, two important features can
be found. One is that the extrapolation of the AT line back to
H = 0 gives the spin-glass transition temperature TF ⬇ 43 K, FIG. 4. Normalized magnetization curves measured at 5 K for
which is consistent with the observed increase of M共T兲 at the uncompacted sample (solid triangles) and the samples com-
low field (inset of Fig. 2). Another is that the extrapolation of pacted under 2 (solid circles) and 5 GPa (solid squares). Inset: The
the line forward to T = 0 gives a critical cooling field relation of HC1 and HC2 versus compaction pressure at 5 K. The
Hcri ⬇ 33 KOe, which indicates that the surface spin-glass solid lines are guides for the eyes.

092409-2
BRIEF REPORTS
FIG. 5. Exchange field HEB for Fe3O4 5-GPa-nanocompacts at
5 K as a function of the cooling field showing a abrupt decrease of
HEB when the cooling field is above the critical field Hcri. Inset:
Compaction pressure dependence of Hcri. The dashed line is a guide
for the eyes.
Clearly, the magnetic loop shifts more to the left hand with
the increase of the compaction pressure, while the loop of
Fe3O4 uncompacted sample is almost symmetrical without
shift. Moreover, the significant feature of the cooling field
dependence of HEB, as shown in Fig. 5, is that HEB changes
little when the cooling field is below 30 kOe, and then, drops
down abruptly to zero when the cooling field is just above
Hcri, which is consistent with the magnitude extrapolated
from the AT line. In the FC process, a preferred configuration
is imposed upon the spin-glass-like surface spins. When the
cooling field is removed, the FM core with a higher ordering
temperature experiences the field generated by the frozen
surface spin-glass-like layer in the direction of the previously
applied field, resulting in the observed shift of the hysteresis
loop below TF, i . e., the hysteresis loop offset arises from the
exchange coupling between the spin-glass-like surface and
core spins. Considering the random-field model of exchange
anisotropy, developed for a ferromagnetic-antiferromagnetic
(FM/AFM) system,16 the relationship of a 1 / tFM dependence
of HEB will be obeyed, where tFM is the thickness of the FM
layer. Thus the little change of HEB is due to the nearly
unvarying thickness of the FM core size.17
It is well known that the smaller the grain size, the larger
the surface distortion. The core-shell structure can be found
in many magnetic oxides, if their sizes are small enough. Our
*Corresponding author. Email address: tzhu@aphy.iphy.ac.cn
1 Magnetic
Properties of Fine Particles, edited by J. L. Dorman
and D. Fiorani (North-Holland, Amsterdam, 1992).
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PHYSICAL REVIEW B 70, 092409 (2004)
experiments have demonstrated the high-pressure-induced
surface effect in magnetic nanosized oxides. When the nano-
particles are compressed by high pressure, a certain surface
layer will be formed, having multiple spin configurations (or
disorder) that can be frozen below the freezing temperature
TF. The reason for the formation of surface spin disorder is
not clear yet, but broken bonds or the translational symmetry
breaking of the lattice at the surface during the compaction
may generate such disorder in the surface. Although it is also
difficult to directly assert that disorder is confined in a
well-limited surface layer or that disorder progresses from
the inner part of the particles to the surface, the core-shell
structure model is still suitable for the Fe3O4 nanoparticles
compacted under high pressures and consistent with the re-
sults of the temperature dependence of FC magnetization.
The observations of the hysteresis loop shift and the abrupt
disappearance of the exchange bias effect near the critical
field clearly reinforces the above discussions. Furthermore, it
is also easy to propose that such a spin-glass-like shell is
related with the compaction pressure, because of the trend of
TF and Hcri to increase with the compaction pressure. If the
external magnetic field overcomes the average random aniso-
tropy of the surface spin-glass-like shell, the surface mo-
ments should be aligned with the core moments in the exter-
nal field, and thus, the surface spin-glass behavior
disappears. Moreover, the surface layer formed under high
pressure will also be considered to be much different from
the normal surface layer of the very fine magnetic oxide
grains, so the critical cooling field for the disappearence of
the surface spin-glass layer in the present Fe3O4 high-pressed
nanocompacts will be much smaller than that in normal very
fine magnetic oxides.
IV. CONCLUSION
In conclusion, evidence for the existence of a low tem-
perature surface spin-glass layer in Fe3O4 high-pressed nano-
compacts has been found. It is demonstrated that a core-shell
structure in the Fe3O4 nanocompacts arises during the com-
paction, which is evident from the field dependence of the
freezing temperature TF following the well known AT line
and obvious exchange bias effect.
ACKNOWLEDGMENTS
This work was supported by NSFC (Grant No. 50171078)
and Chinese Academy of Sciences. One of the authors
(H.W.), thanks Professor J.R. Sun for his helpful advice.
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