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Strongly exchange coupled inverse ferrimagnetic soft/hard, MnxFe3
xO4/
FexMn3
xO4, core/shell heterostructured nanoparticles†
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opez-Ortega,a M. Estrader,*ab G. Salazar-Alvarez,b S. Estrad
e,cd I. V. Golosovsky,e R. K. Dumas,f

A. L

D. J. Keavney,g M. Vasilakaki,h K. N. Trohidou,h J. Sort,ij F. Peir
o,c S. Suri~nach,j M. D. Bar
oj and J. Nogu
esai
Received 24th April 2012, Accepted 13th June 2012
DOI: 10.1039/c2nr30986f

Inverted soft/hard, in contrast to conventional hard/soft, bi-magnetic core/shell nanoparticles of

MnxFe3
xO4/FexMn3
xO4 with two different core sizes (7.5 and 11.5 nm) and fixed shell thickness
(0.6 nm) have been synthesized. The structural characterization suggests that the particles have an
interface with a graded composition. The magnetic characterization confirms the inverted soft/hard
structure and evidences a strong exchange coupling between the core and the shell. Moreover, larger
soft core sizes exhibit smaller coercivities and loop shifts, but larger blocking temperatures, as expected
from spring-magnet or graded anisotropy structures. The results indicate that, similar to thin film
systems, the magnetic properties of soft/hard core/shell nanoparticles can be fine tuned to match
specific applications.

1. Introduction unprecedented control of the structural parameters (e.g., size,

shape and composition) of the particles which leads to the
Core/shell (CS) nanoparticles are an efficient way to construct possibility to fine tune the different functionalities of these
multicomponent systems that combine the distinct properties of multiphase systems.2–4 In the search for materials suitable for
the diverse constituents in a single structure.1 Importantly, the permanent magnets, biomedical applications, sensing applica-
advantage of multicomponent nanostructures lies not only in tions, and future magnetic recording media, bi-magnetic CS
their multifunctionality, but also in the possibility to improve nanoparticles, where both core and shell are magnetic materials,
and tune the single-phase properties using the interactions are attracting a great deal of interest, particularly since an
between the different components. Moreover, the recent inherent exchange bias can be used to overcome the super-
advances in wet chemistry synthesis have allowed an paramagnetic limit.5 In this context, standard and ‘‘inverse’’ bi-
magnetic CS systems involving antiferromagnetic (AFM) and
a
CIN2(ICN-CSIC) and Universitat Aut onoma de Barcelona, Catalan ferromagnetic (FM) phases structured as FM/AFM or AFM/
Institute of Nanotechnology, Campus de la UAB, 08193 Bellaterra FM have been extensively studied in the recent years.6–14 Inter-
(Barcelona), Spain. E-mail: [email protected] estingly, the so-called ‘‘exchange-spring’’ magnets,15 where hard
b
Department of Materials and Environmental Chemistry, Stockholm and soft magnetic phases are exchange coupled, have been the
University, 10691 Stockholm, Sweden
c focus of renewed effort in thin film systems for recording appli-
LENS-MIND-IN2UB, Departament d’Electr onica, Universitat de
Barcelona, Mart
ı i Franques 1, E-08028 Barcelona, Spain cations,16 although less attention has been paid to the case of
d
TEM-MAT, SCT, Universitat de Barcelona, Barcelona, Spain nanoparticles.17 These bi-component materials can exhibit the
e
St Petersburg Nuclear Physics Institute, Gatchina, 188300 St Petersburg, desirable properties of both phases, i.e. large coercivities and
Russia large magnetization arising from the hard and soft phases,
f
Department of Physics, University of Gothenburg, 41296 Gothenburg,
Sweden
respectively.15 Hard–soft nanocomposites such as FePt–Fe3Pt,18
g
Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois NdFeB–FeCo,19,20 NdFeB–Fe,21,22 FePt–Fe3O4 (ref. 23 and 24)
60439, USA and FePt–CoFe2O4 (ref. 25) heterodimers have been prepared by
h
Institute of Materials Science, NCSR ‘‘Demokritos’’, 153 10 Aghia mechanical milling,19–21 self-assembly processes18 or wet-chem-
Paraskevi, Attiki, Greece istry.22–25 However, the limited intimate contact between both
i
Instituci
o Catalana de Recerca i Estudis Avançats (ICREA), Barcelona,
Spain phases in heterodimer systems and the reduced homogeneity in
j
Departament de F
ısica, Universitat Aut onoma de Barcelona, 08193 the case of nanocomposites and self-assembly processes make
Bellaterra, Spain these materials non-ideally suited to accomplish strong exchange
† Electronic supplementary information (ESI) available: Simulated coupling and enhanced properties. In this regard, core/shell
elemental quantification at a given core/shell structure, XAS and
nanoparticles, where the interface contact is maximized, would
XMCD spectra of CS2 nanoparticles and hysteresis loops after FC and
ZFC for both CS1 and CS2 samples. See DOI: 10.1039/c2nr30986f be more adequate. Hard/soft core/shell nanoparticles composed

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of FePt/Fe3O4,24,26–30 Fe/Fe3O4,31,32 CoFe2O4/MFe2O4 (M ¼ Zn, temperature. Two different CS particles were obtained based on
Mn, Fe)33 and Sm(Co1
xFex)/Fe3O4 (ref. 34) have shown, in two seeds, i.e. CS1 (from the large seed1) and CS2 (from the
some cases, an enhanced energy product of the bi-component small seed2). Both the Fe3O4 seeds and the CS nanoparticles were
system over the hard single phase.25,32,35 On the other hand, washed by several cycles of coagulation with ethanol, centrifu-
‘‘inverse’’ soft/hard core/shell configurations have been less gation at 2000  g, disposal of supernatant solution and re-
studied, and only a few examples, FePt/CoFe2O4,30 MFe2O4/ dispersion in hexane.
CoFe2O4 (M ¼ Zn, Mn, Fe)33 and g-Fe2O3/CoFe2O4,36 have
been reported. There are a number of issues that are well known
2.2. Characterization
from thin film studies on spring-magnets that have not been
addressed in nanoparticles. Amongst these are the strong Transmission electron microscopy. TEM images were obtained
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dependence of the properties on the thickness of the two using a Jeol JEM-2010 microscope with a LaB6 filament and a
constituents37 and the enhancement of the properties by inter- Jeol-JEM-2010F microscope with a field-emission gun operated
mixed interfaces35 or graded anisotropy (i.e., where the anisot- at 200 kV. The nanoparticles were dispersed in hexane and then
ropy changes continuously from hard to soft).38 placed dropwise onto a holey carbon supported grid. The particle
Herein we present an exhaustive structural and magnetic size of the different samples and its standard deviation were
study of inverted soft/hard core/shell nanoparticles composed of obtained by calculating the average number by manually
MnxFe3
xO4/FexMn3
xO4 with two different core sizes (7.5 and measuring the equivalent diameters of >200 particles from TEM
11.5 nm) and a fixed shell thickness (0.6 nm) obtained by micrographs.
seeded growth of manganese oxide using different Fe3O4
nanoparticles as seeds. The smooth hysteresis loops obtained X-ray diffraction. XRD patterns were collected using a Pan-
from magnetometry and the compelling similarity between the alytical X’Pert Pro diffractometer with Cu Ka radiation. The
element resolved loops obtained by soft X-ray magnetic circular measurements were carried out in a range of 10–100 2q in steps
dichroism indicate a strong core/shell exchange coupling. of 0.012 and collection time of 300 s. All diffraction patterns
Furthermore, we show that the magnetic properties, e.g., satu- were analyzed using the FullProf code.41 Note that a simple
ration magnetization, coercivity, loop shift or blocking fitting of the diffraction patterns by the Rietveld method using
temperature, are easily controlled by adjusting the size of the an isotropic approximation gives rise to unsatisfactory results
soft core. due to non-uniform size effects. In these cases the numerical
computation of the scattering intensity on the Debye formula
was used.42 The diffraction profiles were satisfactorily described
2. Experimental by implementing an artificial shape (platelet-like) for the shell
component. Finally note that the diffraction signal from the
2.1. Synthesis
shell is exceedingly weak to reliably refine the sizes and
Unless stated, all starting materials were purchased from Sigma- stoichiometry.
Aldrich and used without further purification. The CS nano-
particles were synthesized following an earlier reported proce- Electron energy loss spectroscopy. EEL spectra were acquired
dure where, in two steps, pre-made Fe3O4 nanoparticles were every 0.5 nm along the diameter of the nanoparticles at an energy
used as seeds to subsequently grow a Mn3O4 layer.39 Firstly, range containing the O K, Mn L2,3 and Fe L2,3 edges, with an
Fe3O4 seeds were prepared following a similar method to that energy resolution of 0.8 eV. Mn/O and Fe/O quantifications were
developed by Park et al.40 in which a given amount of iron (III) carried out using the Gatan Digital Micrograph commercial
oleate and 1 mmol of oleic acid were added into 36 mL of software. Importantly, data obtained for different particles of the
1-octadecene. The mixture was heated under magnetic stirring, CS1 sample showed no relevant differences.
with a heating rate of 3  C min
1, up to 320  C and kept for 30
min. The slurry was removed from the heating source and X-ray absorption spectroscopy and X-ray magnetic circular
allowed to cool down to room temperature. Depending on the dichroism. XAS and XMCD measurements were performed on
surfactant-to-metal molar ratio, [S]/[M], different particle sizes dried CS nanoparticles spread onto carbon tape at the 4-ID-C
were obtained. Two [S]/[M] ratios were studied: [S]/[M] ¼ 0.6 beamline of the Advance Photon Source of the Argonne
(seed1 – large particles) and [S]/[M] ¼ 0.3 (seed2 – small National Laboratory. Both XAS and XMCD spectra were
particles). recorded at the Fe and Mn L2,3 edges using total electron yield
Subsequently, the heterogeneous growth of the manganese (TEY) mode at 10 K in a magnetic field of 50 kOe after field
oxide layer was carried out at the surface of the two different cooling (FC) from 300 K under an applied field of 50 kOe. The
seeds following a slightly modified literature process by adding element resolved XMCD hysteresis loops, for the Fe and Mn L3
42 mg of initial seeds in a solution containing 0.6 mmol of edges, were acquired by recording the field dependence of the
manganese (II) acetylacetonate, 0.6 mmol of 1,2-hexadecanediol, XMCD signals at the energies corresponding to the three main
0.3 mmol of oleylamine, 0.3 mmol of oleic acid and 40 mL of peaks of the Fe-edge (i.e., 707.6, 708.7, 709.3 eV) and for the
dibenzyl ether.39 The slurry was mechanically stirred and heated, main energy of the Mn edge (640.1 eV). The XMCD signal was
under an Ar controlled atmosphere, with a heating rate of 10  C normalized by the area of the XAS spectra after correcting for
min
1, to 200  C and kept for 1 h. The flask was removed from the background. Note that since the Fe edge loops at the different
the heating source and cooled down in Ar to 180  C. The solution energies were analogous only the one at E ¼ 709.3 eV is used in
was then exposed to air and allowed to cool to room the discussion.

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X X X
Magnetic measurements. The magnetic properties of the H ¼
Jcore ~i $S
S ~j
JIF ~i $S
S ~j
Jshell ~i $S
S ~j
nanoparticles were measured on tightly packed powdered i; j˛core i˛core; j˛shell i; j˛shell
samples using a superconducting quantum interference device
X 2 X 2 X 2
(SQUID, Quantum Design) magnetometer with a 70 kOe
Kcore ~i $^
S ei
KIF ~i $^
S ei
Kshell ~i $^
S ei
maximum field. The magnetization versus temperature i˛core i˛IF i˛shell
measurements were performed in zero field cooled (ZFC) and
X 2 X
field cooled (FC) conditions in 50 Oe. After FC in 20 kOe from
Ksrf ~i $^
S ~
ei
H$ ~i :
S (3)
300 K to 10 K, hysteresis loops were measured at different i˛srf i
constant temperatures. Moreover, hysteresis loops were also
Here Si and e^i are the atomic spin and the unit vector in the
measured at 10 K after ZFC from 300 K.
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direction of the easy axis at site i. The first three terms give the
In addition to standard major loop measurements, a first-
Heisenberg nearest neighbor exchange interaction between
order reversal curve (FORC)43–46 analysis was conducted using
the spins in the core, in the shell and at the interface. We set
the following procedure. After positive saturation the applied
exchange coupling as Jcore ¼
0.01J in the core, where J is defined
field is reduced to a given reversal field, HR. From this reversal
as a dimensionless ferromagnetic exchange coupling constant taken
field the magnetization is then measured back towards positive
as J ¼ 1, JIF ¼ 4  Jcore at the interface and smaller in the shell
saturation, thereby tracing out a single FORC. This process is
(Jshell ¼ 0.5  Jcore) to account for its lower transition temperature.
repeated for a series of decreasing reversal fields, thus filling the
The following four terms are the anisotropy energies of the core,
interior of the major hysteresis loop, which can be seen as the
the interface, the shell and the surface, respectively. The anisotropy
outer boundary of the family of FORCs. The FORC distribution
is assumed uniaxial and directed along the z-axis in the core, the
is then defined as a mixed second order derivative of the
shell and at the interface and random at the surface. The last term is
normalized magnetization:
the Zeeman energy. The anisotropies in the conventional core/shell
1 v2 MðH; HR Þ=MS structure are taken as Kcore ¼ 0.01J, KIF ¼ 0.03J, Kshell ¼ 0.08J and
rðH; HR Þh
; (1) Ksurf ¼ 0.6J, respectively.
2 vHvHR
Importantly, to account for the chemical gradients, we also
which is then plotted against (H, HR) coordinates on a contour considered the case of graded anisotropy, similar to thin film
map. For a given reversal field, HR, the magnetization is systems.38,47 For such structures, the anisotropy energy term of the
measured for increasing applied fields, H, and therefore H $ HR core or the shell is split into different layers. For example, we have
by design. Following the measurement procedure the FORC considered that the inner core Kcore is maintained constant at 0.01J,
distribution is read in a ‘‘top-down’’ fashion and from left to right while as the layers get closer to the interface the anisotropy grad-
for a particular reversal field. The FORC distribution provides a ually increases as 0.02, 0.03, 0.04, 0.05 and 0.06J (for the top 5
useful ‘‘fingerprint’’ of the reversal mechanism by mapping out, layers in the core) and 0.07 and 0.08J for the shell and finally we
in (H, HR) coordinates, only the irreversible switching maintain Ksurf ¼ 0.6J.
processes. It is often useful to have a one-dimensional visuali- To take into consideration the random distribution of easy
zation of the irreversibility by projecting the FORC distribution axis directions with respect to the applied fields present experi-
onto the HR-axis. This is equivalent to an integration over the mentally, we have calculated hysteresis loops for different angles
applied field H: between the easy axis and the applied field direction. The results
ð for the magnetization are averaged as:
v2 MðH; HR Þ vMðHR Þ 2ðp
dH ¼ ; (2) ðp ðp
vHvHR vHR 1 1
hMi ¼ d4 dqMðqÞcos q ¼ dqMðqÞcos q (4)
4p 2
and is termed a FORC-switching field distribution (FORC- 0 0 0
SFD).
Note that the different parameters are given with respect to J,
Monte Carlo simulations. Monte Carlo simulations were i.e., the field H is given in units of J g
1 mB
1, the temperature T in
carried out considering a single spherical nanoparticle of radius units J kB
1 and the anisotropy coupling constants K in units of J.
R, expressed in lattice spacings, on a simple cubic lattice, with The magnetization M is normalized to the saturation magnetiza-
FiM order. The nanoparticle consists of a soft core (either 10.7 or tion, MS.
16.7 lattice spacings) and a hard shell of thickness equal to 3 The Monte Carlo simulations are performed using the
lattice spacings. The outer layer of one lattice spacing is Metropolis algorithm48 where the microstructure and the temper-
considered to be the surface of the nanoparticle. We use atomic- ature are explicitly included. We perform our calculations of the
scale modeling where the spins in the particle interact with hysteresis loops at a low temperature after a field cooling procedure
nearest neighbors Heisenberg exchange interaction, and at each at a constant rate for a cooling field of HFC ¼ 0.4 J g
1 mB
1, which
crystal site they experience a uniaxial anisotropy. We consider is in the same field range as the one used experimentally.
the size of the atomic spins in the two sublattices of the FiM
particle equal to 1 and 3/2, respectively, for both the core and the 3. Results and discussion
shell. The energy of the system includes the exchange interaction
3.1. Structural and morphological characterization
between the spins in the nanoparticle and the single-site anisot-
ropy energy terms. In the presence of an external magnetic field, Fig. 1 shows the transmission electron microscopy (TEM) images
the total energy of the system is: of the Fe3O4 seeds (Fig. 1a and b for samples seed1 and seed2,

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respectively) and the CS nanoparticles (Fig. 1c and d for samples diffraction spots attributed to an iron oxide cubic spinel phase
CS1 and CS2, respectively). Particle size histograms of both the [(111)c d ¼ 0.481 nm, (220)c d ¼ 0.290 nm, (311)c d ¼ 0.248 nm
seeds and the CS nanoparticles are depicted in Fig. 1e and f and (331)c d ¼ 0.180 nm (JCPDS card no. 82-1533)] and a
corresponding to samples seed1–CS1 and seed2–CS2, respec- manganese oxide tetragonal spinel phase [(200)t d ¼ 0.288 nm,
tively. As can be seen, all histograms are well fitted by a Gaussian (211)t d ¼ 0.248 nm, (004)t d ¼ 0.237 nm and (204)t d ¼ 0.183 nm
distribution, showing a unique size population, with a narrowly (JCPDS card no. 24-0734)] can be observed. Remarkably, while
distributed diameter (deviation <10%). After the growth of the the tetragonal (200)t, (211)t and (204)t diffraction planes overlap
Mn oxide layer, the diameter of the CS nanoparticles becomes with the cubic (220)c, (311)c and (331)c ones, the plane (004)t
8.6(0.6) (CS2) and 12.6(1.0) (CS1) compared to the initial 7.5(0.6) (highlighted by arrows in Fig. 2e and f) belongs only to a
nm (seed2) and 11.5(0.9) nm (seed1), respectively. Importantly, tetragonal spinel phase.
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upon comparing the sizes of the seeds and CS nanoparticles, The analysis of the XRD patterns corresponding to the iron
there is a clear shift of 1.1 nm to larger diameters both for CS1 oxide seeds and the CS nanoparticles (Fig. 3) revealed that the
and CS2 samples, indicating that a Mn oxide shell of roughly sizes of the seeds are similar to the corresponding core sizes of the
0.6 nm thickness is indeed grown on top of the seeds. Moreover, CS nanoparticles (see Table 1). Moreover, these values are
the similarity between the thicknesses of the two shells suggests consistent with those obtained from TEM analysis. Interestingly,
that the seed-growth procedure does not depend strongly on the the refinement of the site occupancies shows that both the core
initial seed size. and the seeds have a near stoichiometric spinel Fe3O4 composi-
High resolution TEM (HR-TEM) images of seed2, CS1 and tion. However, there are small differences in the occupancy of the
CS2 and their respective fast Fourier transform (FFT) are shown seeds, i.e., (Fe0.82(1))[Fe0.90(1)]2O4 and the CS particles, i.e.,
in Fig. 2. The FFT analysis obtained from the HR-TEM images (M0.90(1))[M0.96(1)]2O4 (M ¼ Fe and Mn) which imply that
of the CS samples (Fig. 2e and f) confirms the presence of a new probably some Mn ions have diffused into the core during the
phase in contrast to the data of the seeds which display a purely synthesis of the CS particles. Note that it is not possible to
cubic structure (Fig. 2d). In both CS samples two sets of different distinguish between iron and manganese ions using X-rays, hence
it is difficult to give a more quantitative account of the manga-
nese diffusion. A comparison of the refined cell parameters for
the core with the reported values for the Mn3O4–Fe3O4 system49
indicates that the core can incorporate up to 50% of Mn atoms.
Concerning the shell, the comparison of the obtained cell
parameters with the literature values49 unambiguously evidences
that in sample CS1 about 10% of manganese ions of the Mn3O4
shell are substituted by iron ions, while maintaining the Mn3O4
tetragonal structure.
In order to gain further insight into the structure of the CS
particles, the local electron energy loss spectra (EELS) were
analyzed by evaluating the M–L2,3 onset and the M/O ratio (M ¼
Mn and Fe) to obtain the distributions of the different ions
across the particles, see Fig. 4. The EELS analysis reveals the
presence of two clearly differentiated regions in the particle, i.e.,
a core and a shell, the former being iron rich and the latter one
manganese rich. However, remarkably, both iron and manga-
nese ions were found across the whole particle (Fig. 4e). Bearing
in mind these results, together with the XRD and FFT studies
where the existence of a tetragonal spinel phase was confirmed,
different CS structures (i.e., sizes and compositions) were simu-
lated to match the observed metal distribution. The best corre-
spondence was found for a MnFe2O4(10.2 nm)/
FeMn2O4(1.2 nm) CS structure, as schematically shown in
Fig. 4b, with an iron rich core and a manganese rich shell.
Interestingly, using compositional gradients throughout the
particles (rather than fixed core/shell structures) e.g.,
Mn0.75Fe2.25O4(8 nm)/Fe1.75Mn1.25O4(0.6 nm) shell
1/Fe1.5Mn1.5O4(0.6 nm) shell 2/Fe0.75Mn2.25O4(0.6 nm) shell 3,
leads to a further improvement of the agreement between the
simulated and experimental results (see Fig. S1 in the ESI†). It is
known that mixed spinel phases can preserve their initial crystal
Fig. 1 TEM images of iron oxide seed particles, (a) seed1 and (b) seed2 symmetry before reaching a critical doping value, for instance
and of the corresponding CS nanoparticles, (c) CS1 and (d) CS2. MnFe2O4 (Fd3m) and FeMn2O4 (I41/amd) would keep the cubic
Histograms of the different nanoparticles, (e) seed1–CS1 and (f) and tetragonal structure of Fe3O4 and Mn3O4, respectively.49
seed2–CS2. The results indicate that an interdiffusion of iron and manganese

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Fig. 2 HR-TEM images of (a) seed2, (b) CS1 and (c) CS2 nanoparticles together with their respective FFT analysis, (d–f). The diffraction spots in FFT
images for cubic and tetragonal structures are marked with c and t, respectively. The pure tetragonal spots are highlighted by arrows.

can be attributed to a soft annealing while exposing the slurry to

air at 180  C. Note that the nanoparticles in sample CS2 dis-
played a rather poor signal-to-noise ratio since, given the small
size of CS2 nanoparticles, the signal at the Fe- and Mn-edges was
rather weak compared to the carbon signal arising from the
organic surfactants and thus the EEL Spectra for CS2 were not
analysed.
Additional evidence for the graded composition of the CS
particles was obtained by using X-ray absorption spectroscopy
(XAS) and X-ray magnetic circular dichroism (XMCD).
Importantly, the total electron yield (TEY) mode depends on the
probing depth (lx), which for soft X-rays can be taken to be of
the order of 10 nm for most metal oxides.51 Assuming such lx and
that the nanoparticles are composed of, approximately, 85%-
MnFe2O4/15%-FeMn2O4, the spectra should be understood as a
convolution of the signal from the shell and the core. Fig. 5
shows an example of XAS and XMCD spectra obtained at Fe
Fig. 3 Profile analysis of the X-ray diffraction patterns from seed1 (a)
and Mn L2,3 edges for sample CS1. From the theoretical XAS
and the CS1 nanoparticles (b). The observed profile (in red) and the
spectra of Fe2+ ions in octahedral and Fe3+ ions in octahedral and
calculated (in blue) are both shown in the graphs. The vertical bars mark
the position of Bragg reflections as indicated.
tetrahedral environments, the peak I1 in Fig. 5b can be associated
to the presence of Fe2+ in Oh positions while peak I2 correlates to
Fe3+ ions located in Oh and Td environments.52 By analyzing the
 for the different seeds
Table 1 Unit cell parameters and sizes (both in A)
and CS nanoparticles. The figure in parenthesis corresponds to the
ratio of the different peak intensities, I1/I2, it is possible to obtain
standard deviation in the last digit qualitative information about the cation concentration in each
oxide phase.53 Given the structure of Fe3O4, (Fe3+)[Fe3+Fe2+]O4,
Core Fe3O4 Shell Mn3O4 and g-Fe2O3, (Fe3+)[Fe3+5/3,1/3]O3 one would expect I1/I2 ratios
Sample a Size a c of 0.53 and 0.19 for Fe3O4 and g-Fe2O3, respectively.51 The
experimental I1/I2 value for both samples CS1 and CS2 is 0.4.
CS1 8.3801(6) 93(1) 5.767(1) 9.414(2) This implies that the samples have an intermediate composition
Seed1 8.3501(5) 91(2) between g-Fe2O3 and Fe3O4. Therefore, the presence of a
CS2 8.3803(5) 73(1) 5.775(1) 9.432(2)
Seed2 8.343(1) 68(3) MnFe2O4 structure, (Fe3+)[Fe3+Mn2+]O4,52,54 without Fe2+ ions in
octahedral positions, would fit adequately in this scenario in
agreement with the EELS results (particularly assuming that due
ions between core and shell has taken place leading to mixed to the thin shell with small iron content most of the XAS iron
Fe–Mn spinel CS particles.50 The ion diffusion and the signal arises from the core). On the other hand the XAS spectrum
concomitant change in the composition of the CS nanoparticles at the Mn L2,3 edge (Fig. 5a) resembles that of pure tetragonal

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Fig. 5 (Top) XAS and (bottom) XMCD spectra at the (left) Mn and
(right) Fe edges of CS1 nanoparticles.

edge (Fig. 5c) cannot be associated to any single phase and can be
clearly ascribed to a mixed XMCD signal, e.g., arising from
Fig. 4 (a) High-angle annular dark field (HAADF) image of CS1 tetragonal FeMn2O4 and cubic MnFe2O4 oxide structures.55
nanoparticles, where the approximate positions where the local spectra Note that the lack of XMCD studies at the Mn L2,3 edge on pure
were obtained are shown by a green arrow. (b) Schematic representation FeMn2O4 (in bulk or nanoparticle form) makes a more detailed
of the CS nanoparticles simulated from the EELS analysis. (c) and (d) analysis rather complex. Similar results were found for CS2
show EELS spectra for the shell and core, respectively, as indicated by nanoparticles, both for the XAS and XMCD analysis, see
yellow and red arrows, respectively, in (a). (e) Elemental quantification Fig. S2†.
along the particle diameter for Fe (squares), Mn (triangles) and O
(circles). The solid lines represent the simulated elemental profile for a
particle with a MnFe2O4(10.2 nm) core/FeMn2O4(1.2 nm) shell structure. 3.2. Magnetic properties
Fig. 6a shows the ZFC/FC magnetization curves for the CS1 and
Mn3O4, (Mn2+)[Mn3+]2O4.55 However, it has a lower intensity CS2 nanoparticles. Although at high temperatures both samples
ratio, I0 1/I0 2 ¼ 0.7, than expected for Mn3O4, i.e., I0 1/I0 2 ¼ 0.87, exhibit the characteristics of superparamagnetic systems57 with
but larger than the corresponding one for MnFe2O4, I0 1/I0 2 ¼ blocking temperatures, TB,1CS1 ¼ 205 K and TB,1CS2 ¼ 115 K,
0.5.54 Hence, the Mn L2,3 signal can be understood as a mixed both systems exhibit a second transition at TB,2  40 K.
signal arising both from the shell, close to a tetragonal FeMn2O4 However, the features at TB,2 are more evident for CS2. More-
phase, and the core, with a cubic MnFe2O4 structure. over, as can be seen in Fig. 6b, the low temperature (10 K)
Concerning the XMCD spectra, the signal of the iron edge hysteresis loops show that the saturation magnetization, MS, for
(Fig. 5d) is somewhat consistent with those of pure cubic spinel CS1 (MSCS1 ¼ 48 emu g
1) is higher than that for CS2 (MSCS2 ¼ 40
iron oxides (Fe3O4 and g-Fe2O3) spectra,53 although some small emu g
1). Upon enlarging it becomes clear that the loops are
deviations attributed to the presence of the mixed MnFe2O4 rather smooth, i.e., no kinks – typical of two phase systems –15
oxide can be observed. Concretely, the different intensity peak can be observed, Fig. 6b. Interestingly, both samples exhibit a
ratios of the first two peaks of the iron XMCD signal with respect loop shift in the field axis, HE (i.e., exchange bias), with respect to
to pure iron oxides can be interpreted in the same way as the the zero field cooled loop (Fig. S3†), and moderate coercivities,
XAS analysis regarding the concentration of Fe2+ ions in octa- HC,6 that vanish around 50–60 K, both parameters being larger
hedral positions.54,56 In contrast, the spectrum at the manganese for CS2 (Fig. 7).

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Fig. 7 Temperature dependence of (a) the coercivity, HC, and (b) the
loop shift, HE, for CS1 and CS2 nanoparticles. The lines are guides to the
eye.

Fig. 6 (a) Temperature dependence of the field cooled (FC) and zero exhibited by CS1 is consistent with its larger core, since the
field cooled (ZFC) magnetizations and (b) an enlarged view at low field of relative contribution of the shell (with a smaller MS than that of
the hysteresis loops at 10 K for CS1 and CS2 nanoparticles. The inset the core62) should be smaller for larger particles. This core/shell
shows the hysteresis loops in the full field range. volume ratio also explains the more prominent features at TB,2
shown by CS2.
Concerning the presence of exchange bias and moderate
These results are consistent with the proposed MnxFe3
xO4/ coercivities, although these effects are expected for an exchange
FexMn3
xO4 core/shell structure. Concerning the different TB, coupled antiferromagnetic AFM/FM systems, they can also be
the high temperature ones (TB,1) could be related to the cubic found in coupled soft FiM (or FM) and hard FiM (or FM).6 In
ferrimagnetic (FiM) MnxFe3
xO4 phase that constitutes the core the current core/shell nanoparticles, assuming the composition of
of the nanoparticle, while the low temperature one (TB,2) to the the shell is in the range Mn3O4–FeMn2O4, at 10 K the anisotropy
tetragonal FiM FexMn3
xO4 phase forming the shell. Thus, the would be expected to be about |Kshell| 5  105 to 1  106 erg
lower TB,1 for CS2 can be easily explained by its smaller core cm
3.58,63,64 In contrast, if the core composition is in the range
volume since TB ¼ KV/25 kB,57 (where K is the magnetic Fe3O4–MnFe2O4, the corresponding anisotropy would be |Kcore|
anisotropy, V the volume and kB the Boltzmann constant). In 2  105 erg cm
3.58,65 Consequently, our core/shell particles can
fact, assuming that the anisotropies remain the same in both be considered as an ‘inverted’ soft/hard system, although the
cores, the ratio TB,1CS2/TB,1CS1 leads to a volume ratio in rough difference in Kshell
Kcore may not be as large as in some of the
concordance with the initial seed sizes. In principle, similar typical hard/soft spring-magnet systems.15
effects should occur for TB,2 since, although the shell thickness is In AFM/FM thin film systems it is well established that HC
the same for both systems, the core sizes vary and the corre- and HE are inversely proportional to the thickness (size) of the
sponding shell volumes should be different. The origin of this FM phase. Thereby, by drawing an analogy, in soft/hard systems
TB,2 is probably two-fold. First, FeMn2O4 is known to have a it is accepted that HC, HE f 1/size(soft-FM). Thus, the smaller HE
very strong temperature dependence of K, with a sharp increase and HC for CS1 arise from the larger diameter of its core. Finally,
in K around 50–60 K.58,59 Thus, when K reaches a certain the temperature dependence of HC and HE is controlled by the
threshold the system becomes blocked. Moreover, since the phase with lowest TB, i.e., the hard shell phase, in analogy with
FexMn3
xO4 shell phase exhibits a tetragonal structure with a most of the standard AFM/FM systems.6 Interestingly, the
non-stoichiometric structure, probably close to that of Mn3O4 coercivity of both CS particles is relatively small compared with
(as hinted from the XRD lattice parameters and the EELS that expected for Mn3O4–FeMn2O4 (forming the shell).12 In
graded composition simulation), a magnetic behaviour similar to analogy with thin film systems, this implies that the soft core and
that of Mn3O4 could be expected. In this sense, the second the hard shell are strongly exchange coupled as expected from
temperature transition present in both samples, TB,2  40 K, their small size (smaller than the domain wall width) and their
would be consistent with the TC ¼ 40 K of bulk Mn3O4, as similar anisotropies.15,37 This leads to smooth loops with
expected from the strong dependence of TC on the Mn content increased MS and reduced HC, with respect to the pure hard
for Mn-rich FexMn3
xO4.49,60,61 Similarly, the larger MS Mn3O4 phase.

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 View Article Online

To gain further insight into the core/shell structure of the

nanoparticles, we acquired element-specific XMCD hysteresis
loops at the iron and manganese edges (shown in Fig. 8).
Although the overall shape of the XMCD hysteresis loops at
both edges is rather similar, their approach to saturation shows
clear differences. Namely, the loop taken at the iron edge satu-
rates at considerably lower fields than the loop corresponding to
manganese (see Fig. 8 for CS1). Remarkably, HC of both
elements is similar for both samples. However, while for CS1
HC(Mn) and HC(Fe) are roughly the same, within the error, for
Published on 18 June 2012. Downloaded by Universitat des Saarlandes on 11/10/2016 13:44:35.

CS2 HC(Mn) is slightly larger than HC(Fe) (see inset in Fig. 8).
These results are in concordance with the magnetometry
hysteresis loops where CS2, with proportionally more Mn,
exhibits both an enhanced HC and larger saturation field than
those of CS1. The element resolved loops allow us to assign these
features to the presence of a magnetically harder manganese-
based phase. Given that, nominally, the iron and the manganese
hysteresis loops should mainly correspond to the core and the
shell, respectively, the element specific hysteresis loops confirm
the inverse soft/hard core/shell structure of the nanoparticles.
Importantly, the similarities between the Fe and Mn contribu-
tions to the hysteresis loops imply again a strong coupling
between the core and the shell. However, the concomitant
overlap of diverse contributions in the XMCD spectra (due to
simultaneous interdiffusion of iron and manganese ions between
the core and the shell) makes a quantitative analysis rather
complex.
The coupling between the core and shell is further investigated
by analyzing the first order reversal curves (FORC). The
measured family of FORC curves is shown in Fig. 9a and b for
samples CS1 and CS2, respectively. The major loop, seen as the
outer boundary of the FORCs, shows the expected exchange
bias. The resultant FORC distributions, shown as insets in
Fig. 9a and b, are both broad single peaks, consistent with prior
nanoparticle FORC distributions.44 The broadness of the peaks
can be attributed to distributions in size, anisotropy easy axis Fig. 9 Families of FORCs, whose starting points are represented by
direction and strength, and exchange coupling. The FORC black dots, for samples (a) CS1 and (b) CS2 with the corresponding
switching field distributions (FORC-SFDs), plotted in Fig. 9c, FORC distributions plotted in (H, HR) coordinates shown as insets. The
show a clear asymmetry for both the CS1 and CS2 samples, resultant FORC-SFDs are shown in (c).
where the initial rapid onset of reversal (HR  +500 Oe) is
followed by a more gradual and extended switching tail towards
negative HR values. Similar asymmetric FORC-SFDs have been
observed in hard/soft and graded anisotropy composite
films38b,45,46 where the extended hump can be attributed to the
more negative HR needed to switch the high anisotropy
components. Note that single phase nanoparticles similar to the
core (i.e., without shell) exhibit symmetric peaks in the FORC-
SFD. Interestingly, sample CS2 approaches negative saturation
more gradually than CS1, suggesting a more dominant hard
phase component, which is also consistent with the larger
exchange bias and coercivity observed in this sample at 10 K.
The hysteresis loops were simulated by using Monte Carlo
based on a (a) conventional core/shell model (i.e., a single value
for the interface anisotropy; Fig. 10a) (b) a graded anisotropy
model (Fig. 10b). As can be seen in the figures, both approaches
Fig. 8 Element resolved XMCD hysteresis loop at the iron edge capture the main features of the experimental loops. For
(709.3 eV – open symbols) and manganese edge (640.1 eV – filled example, the smaller nanoparticles exhibit larger HC and HE
symbols) for sample CS1. The inset shows an enlargement of the than the bigger ones. Similarly, in the moderate field range the
hysteresis loops for sample CS2. The lines are guides to the eye. small particles have a broader loop both in the experimental and

This journal is ª The Royal Society of Chemistry 2012 Nanoscale, 2012, 4, 5138–5147 | 5145
 View Article Online

magnetic properties by the soft/hard coupling could render novel

types of core/shell nanoparticles suitable for applications such as
permanent magnets or in magnetic shielding.

Acknowledgements
This work is supported by the 2009-SGR-1292 and 2009-SGR-35
projects of the Generalitat de Catalunya, by the MAT2010-
20616-C02, MAT2011-27380-C02-01, MAT2010-16407 and
CSD2009-00013 projects of the Spanish Ministry of Science and
Published on 18 June 2012. Downloaded by Universitat des Saarlandes on 11/10/2016 13:44:35.

Innovation (MICINN), the ONDA project (no. FP7-PEOPLE-

2009-IRSES-247518) of the European Union and the Russian
grants RFBR-10-02-00576 and MESRF-16.518.11.7034. The
authors thank P. Gambardella and J. J. Kavich for useful
discussions. I. V. G. thanks the Generalitat de Catalunya for his
sabbatical fellowship (2010 PIV 00096). M. D. B. was partially
supported by an ICREA Academia award. Use of the Advanced
Photon Source was supported by the U.S. Department of
Energy, Office of Science, Office of Basic Energy Sciences, under
Contract DE-AC02-06CH11357.

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