Applied Surface Science 253 (2006) 2589–2596

www.elsevier.com/locate/apsusc

Magnetic structure and collective Jahn–Teller distortions in

nanostructured particles of CuFe2O4
I. Nedkov a,*, R.E. Vandenberghe b, Ts. Marinova c, Ph. Thailhades d,
T. Merodiiska a, I. Avramova c
a
Institute of Electronics, Bulgarian Academy of Sciences, 72 Tzarigradsko Choussee Blvd., 1784 Sofia, Bulgaria
b
Department of Subatomic and Radiation Physics, University of Gent, B-9000 Gent, Belgium
c
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Bulgaria
d
Université, ‘‘Paul Sabatier’’, 118 Route de Narbonne, 31 062 Toulouse Cedex 4, France
Received 24 January 2006; accepted 13 May 2006
Available online 7 July 2006

Abstract
The aim of the present work is to compare the structural, the composition and chemical state of the surface and magnetic properties of different
nanosized CuFe2O4 powders exhibiting collective Jahn–Teller effect. The samples under examination consist of edged nanosized particles (needle
like) with average length 1300  20 nm and diameter 300  20 nm obtained after high temperature synthesis, and superparamagnetic (at room
temperature) spherical particles (d = 6  2 nm), obtained by soft chemistry techniques. The surface composition of the particles was investigated
by X-ray photoelectron spectroscopy (XPS). Mössbauer spectroscopy (MöS), including at high magnetic field up to 5 T and 4.2 K, was used for
characterization of cation distribution in the samples. The data yielded by the XPS and MöS analyses for spherical nanosized particles led us to the
assumption for the existence of a Jahn–Teller effect gradient—from the B-sublattice on the surface to a compensation of the tetragonal distortion in
the two sublattices in the core. The analysis of the contribution of the anisotropy energy in edged and spherical nanoparticles shows that it must be
considered as an effective value reflecting the influence of the individual factors depending on the particle shape and surface.
# 2006 Elsevier B.V. All rights reserved.

PACS: 73.22.-f; 71.70.Ej; 71.45.-d

Keywords: Nanostructured particles; Copper ferrite; Surface effects; Collective Jahn–Teller effect; Magnetism; XPS; Mössbauer spectroscopy

1. Introduction
The contribution of superexchanged magnetic interactions
to the formation of magnetocrystalline anisotropy in nanosized
ferroxides with two and more magnetic sublattices is not well
understood. Previous studies [1] have shown that the crystal
sublattice formation in nanosized spherical ferroxide particle
has some specific peculiarities and, with the same stoichio-
metry, the spinel cell is different from that of the bulk material.
The presence of cations provoking collective distortion effect of
the type of Jahn–Teller effect in the spinel crystal is a good
indicator for the extent of these peculiarities in the nanosized
particle. On the other hand, these peculiarities will inevitably
* Corresponding author. Tel.: +359 2 71 44 482; fax: +359 2 975 3201.
E-mail address: nedkov@ie.bas.bg (I. Nedkov).
0169-4332/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2006.05.049
influence the formation of the particle surface layer which has
disordered and unbalanced magneto-crystalline structure which
will ultimately change the magnetic properties of the system as
a whole. The Kodama–Berkowits model [2] explains the
magnetic properties of these particles by the appearance of
‘‘spin-canting’’, which is the cause of the exchange magnetic
interactions between the disordered spin structure of the surface
layer and the antiferromagnetic arrangement of the moments
inside the particle; this cannot, however, account for the
superexchange and structural peculiarities.
At certain technological conditions, the copper and
manganese ions in substituted spinels can provoke a collective
Jahn–Teller effect [3] which is associated with the alignment of
the Cu2+ ions occupying the tetragonally distorted octahedral
spinel lattice formed by the oxygen ions. The copper ferrospinel
is an inverse ferromagnetic spinel. It is considered that the
CuFe2O4 is a ferrite of Cu2+. The cation distribution in this
2590 I. Nedkov et al. / Applied Surface Science 253 (2006) 2589–2596
copper ferrite can be presented by the formula: [Cux2+-
Fe1x3+]A[Cu1x2+Fe1+x3+]BO4. The parameter of inversion, x,
is equal to 0 for inversion spinels and to 1, when the spinel is
normal. Cu2+ cations migrate from octahedral (B-sublattice) to
tetrahedral places (A-sublattice). When the spinel is synthe-
sized using classical ceramic technologies (high temperature
treatment of the initial oxides of the metal cations) with strict
stoichiometry (x = 1), it has a tetragonal structure of
hausmannite type with crystal cell parameters a = 8.20 and
c = 8.60; c/a = 1.05 [4]. According to other authors [5]
a = 8.24, c = 8.68, but c/a is again 1.05. The structure of
CuFe2O4 is considered as that of a tetragonally deformed spinel
stretched along the h0 1 1i direction. The c/a ratio can be
changed via decreasing the copper concentration, or alter-
natively, by temperature treatments. Yokoyama et al. [6]
observed changes in the crystal structure of nanosized CuFe2O4
powders obtained by coprecipitation and subsequently
annealed. They proved that the copper spinel is cubic at
temperatures below 300 8C and tetrahedral over 400 8C.
Although the stable low-temperature phase of this type of
ferrite is tetragonal (c/a  1) a deficit of Cu2+ cations in the B-
sublattice leads to the absence of co-operative-active Jahn–
Teller distortion and the crystal cell transforms into cubic.
According to some authors, the transition from tetragonal to
cubic structure has to do with changes in the oxygen content in
the lattice, i.e. with formation of observable quantities of Cu+.
Kester et al. [7] proved that in the case of the reduction reaction
for quenched samples of CuFe2O4, the mechanism involves the
formation of Cu+. The rate of reduction, i.e. the Cu+ cation
fraction in the B-sublattice strongly depends on the technol-
ogies of synthesis and the subsequent temperature treatment.
Nanosized (10–30 nm) particles of CuFe2O4, obtained by a
classical ceramic technology, have also been studied [8]. The
high temperature treatment of these materials could lead to
structural and magnetic surface disorders. Many reasons, such
as different copper dispersion in the sublattices, appearance of
cations and oxygen vacancies, amorphisation of the structure,
presence of surface layer with crystalline and magnetic
structure different from that of the particles’ core, can cause
these disorders. All these effects [2–4,8,9] strongly impede the
interpretation of the structural influence on the physical
properties of such type of materials.
The aim of the present work is to compare the structural, the
composition and chemical state of the surface and magnetic
properties of different nanosized CuFe2O4 powders exhibiting
collective Jahn–Teller effect. The samples under examination
consist of edged nanosized particles (needle like) with average
length 1300  20 nm and diameter 300  20 nm obtained after
high temperature synthesis, on the one hand, and super-
paramagnetic (at room temperature) spherical particles (d =
6  2 nm), obtained by soft chemistry techniques, on the other.
2. Experimental
Two different methods were used for the synthesis of
CuFe2O4. The first one (sample 1) has been prepared by a ‘‘soft
chemical’’ method—coprecipitation of Fe 2+ and Cu2+cations
in strong alkaline media at room temperature [10,11]. Diluted
water solutions of FeCl24H2O and CuCl22H2O mixed in the
ratio 2/1 with intensive stirring are used for that purpose. In a
water solution, the chlorides of these elements exist in a
complex form. When concentrated solution of NaOH with pH
13 is added, the water complexes turn into hydroxides and a
black precipitate of CuFe2O4 is produced. After decantation the
precipitate is rinsed in distilled water up to pH 7 and then dried
at 50 8C. The particles thus obtained have a spherical shape
(Sp) with average size of 6  2 nm. This sample further on the
text will be indicated as CuFe1-Sp.
The second method was described in [12] and consist of two
main stages: (i) the concentrated solution of cupric and ferrous
is precipitated in oxalic acid at room temperature and (ii) the
oxalic precursors are slowly decomposed in an air flow, treated
at 710 8C for 4 h and slowly cooled (SC) at a rate of 10 8C/h.
This sample will be indicated as CuFe2-SC. Following the same
synthesis the sample which was quenched (Q) from 710 8C to
room temperature is the third object of this investigation and
have been indicated as CuFe3-Q.
The XRD data exhibited consistently a single-phase spinel
structure for all types of samples. The average particle size was
determined by applying Sherrer’s formula from the XRD
spectra with Lorentz broadening and SEM images. Chemical
states of copper ferrite spinel of the particle’s surface were
determined by XPS. The magnetic properties were character-
ized by VSM while the cation distribution in the copper ferrite
spinel structure was obtained by means of Mössbauer
spectroscopy (MöS). Spectra were collected on a conventional
time-mode spectrometer using a 57Co/Rh source. External
longitudinal magnetic field spectra were obtained in a field of
5 T obtained by a split-coil superconducting magnet. The
spectra were analyzed taking hyperfine field distributions into
account where necessary. For the analysis of the external-field
spectra both the hyperfine field and the canting angle have been
considered by using a double distribution [13].
3. Results and discussions
The morphology of the powders was investigated by
scanning electron microscopy (SEM—JEOL JSM 6400) (see
Fig. 1). The X-ray diffraction pattern showed a single-phase
tetragonal structure. The structural studies were presented and
discussed in references [11,12] and showed the presence of a
co-operative Jahn–Teller effect for the of CuFe2O4 stoichio-
metry. The SEM images (Fig. 1) show unambiguously the
difference in the particle shape of samples CuFe1-Sp and
CuFe2-SC. The particle size and shape of sample CuFe3-Q, are
similar to those of sample CuFe2-SC.
The small size and the specific shape of the particles
investigated determine the strong influence of the surface on
their physical properties. This motivated us to carry out a more
detailed study concerning chemical state of constituent
elements of the particles surface. One of the most powerful
and sensitive methods for surface analysis was used for this
purpose, namely, X-ray photoelectron spectroscopy (XPS). The
analyses were performed on a VG ESCALAB Mk II
 I. Nedkov et al. / Applied Surface Science 253 (2006) 2589–2596
Fig. 1. High-resolution SEM images of tetragonal distortion vs. annealing temperature for CuFe2O4: (a) sample CuFe2-SC acicular particles and (b) sample CuFe1-
Sp, spherical particles.
spectrometer using an Al Ka excitation source (1486.6 eV)
with a total instrumental resolution of 1 eV, under a base
pressure of 1  108 Pa. The O 1s, Cu 2p and Fe 2p
photoelectron lines were recorded. All lines recorded were
calibrated to the C 1s line at 285 eV. The surface composition of
the particles was determined from the ratio of the correspond-
ing peak intensities, corrected by the photo-ionization cross-
sections. The spectra are displayed in Fig. 2 (they are compared
with the model spinel structure of magnetite) and the main
results are summarized in Table 1.
The O 1s spectra (see Fig. 2a) exhibit a single peak around
530.1 eV. The Fe 2p3/2 and 2p1/2 main peaks (Fig. 2b) are
accompanied by satellite structures on the higher binding energy
side, at about 8 eV. The binding energy attributed to Fe3+ is about
711.1 eV for CuFe1-Sp and CuFe1-Q. For sample CuFe1-SC it is
710.5 eV; the shoulder on the lower binding energy side of the
main peak evidences some small amounts of Fe2+ ions.
The binding energies for the Fe 2p3/2 level range between
710.5 eV and 711.1 eV. The shift towards higher binding
energies observed for the CuFe1-Sp and CuFe3-Q samples
could be attributed to the presence of very small particles. It is
known that the final state effects in the photoemission process
due to poor screening of the positive hole in particles with small
sizes for the quenched sample could be the reason for this shift
[14,15]. Concerning the Cu 2p spectra, in Fig. 2c one can see
the main peak of Cu 2p3/2 and a satellite located on the higher
Fig. 2. XPS data for: (a) O 1s, (b) Fe 2p and (c) Cu 2p CuFe2O4 samples: (1) CuFe1-Sp, (2) CuFe2-SC and (3) CuFe3-Q compared with XPS of Fe3O4.
2591
binding energy side, indicating that the copper valence is 2+.
For all samples, the main Cu 2p3/2 peak is broad and
asymmetric on lower binding energies side.
Several attempts have been reported to analyze the copper
peak in photoelectron spectra of different copper containing
spinels in terms of a superposition of peaks originating from
copper (Cu2+ and Cu+) cations in octahedral and tetrahedral
environment [16,17]. Many experimental and theoretical
studies of a number of copper compounds have shown a
strong dependence of the core-level photoemission spectrum on
the type of Cu–O network forming the structure of the
compound [18,19]. This made us presume that Cu2+ cations
occupying both tetrahedral and octahedral interstitial sites form
two types of Cu–O networks, which are probably responsible
for the features observed in the spinel systems investigated. For
Cu-containing compounds, the satellite peaks are quite
sensitive to changes in the coordination environment of Cu2+
ions. In particular, the coordination geometry of the surface
Cu2+ ions can be investigated by determining the intensity ratio
of the satellite peaks and the main peaks. Generally, the Isat/Im
ratio decreases as the number of oxygen ions coordinated to a
Cu2+ ion increases [20]. The Isat/Im ratio calculated for the
samples investigated showed that it was close to that for the
bulk CuO standard (0.56) for sample CuFe3-Q only. Bearing in
mind that the coordination number of Cu2+ is six in the distorted
octahedron [21], it is reasonable to suppose that the decrease of
2592 I. Nedkov et al. / Applied Surface Science 253 (2006) 2589–2596

Table 1
XPS data
Sample O 1s (eV) Cu 2p3/2 (eV) Fe 2p3/2 (eV) Cu/Fe Cu (at. %) Fe (at. %) (Isat/Im)Cu
CuI1 (Sp) 530.1 934.2 711.1 0.77 15.8 20.5 0.72
CuFe2 (SC) 530.3 933.6 710.5 0.69 14.7 21.1 0.72
CuFe3 (Q) 530.3 934.2 711.1 0.73 16.1 22.0 0.65
CuO (Merck) 529.9 934.2 0.56

the Isat/Im ratio should be due to an increase in the surface
octahedral Cu species. This leads to the conclusion that there is
a large amount of CuO on the surface of the last spinel (CuFe3-
Q). For the samples with lower surface concentration of Cu
(CuFe1-Sp and CuFe2-SC) the dispersed copper oxide
simultaneously exists in tetrahedral and octahedral coordina-
tion geometry. The XPS data suggest that the linkage Cu–O
probably is different from this one for the bulk material. The
octahedral coordinated surface Cu species is predominant for
the sample (Q) having higher concentration of Cu (see Table 1).
The studies of the particle surface by XPS showed that edged
particles obtained by different temperature treatment, respec-
tively, slow cooling (SC) from 700 8C and quenching (Q)
exhibit different surface structure. For the sample CuFe3-Q
obtained after quenching—the analysis showed the presence of
a second CuO phase on the surface due to the insufficient time
for completing the solid-phase reaction in the synthesis process
[22]. The edged particles (CuFe2-SC) obtained by solid state
reactions at high temperature and slow cooled and the soft
chemistry product—smaller spherical particles (CuFe1-Sp)
show similar surface Isat/Im ratio but different Fe3+ presence.
The data obtained stimulated our interest in further character-
ization of the magnetic properties of edged (sample CuFe2-SC)
and spherical (CuFe1-Sp) particles since the structural analysis
of both types of nanoparticles showed unambiguously a
monophase structure on the surface and the presence of a co-
operative Jahn–Teller effect.
Mössbauer spectroscopy is a widely used tool for the
characterization of nanosized magnetite, the latter being one of
the most interesting magnetic ferrospinels for various applica-
tions. The MöS data for sample CuFe2-SC is shown in Fig. 3.
Fig. 3. Mössbauer spectra at room temperature of sample CuFe2-SC—edged
particles with size 1300  20/200  20 nm.
Table 2 shows the hyperfine parameters of the sample
CuFe2-SC with edged particles.
The MöS data processing showed the following cation
distribution for the sample CuFe2-SC:
Sample CuFe2 -SC
: ðFe0:91 Cu0:09 ÞA ½Fe1:09 Cu0:91 B O4 ðtetragonal c=a > 1Þ
These structural formulae allowed the elementary magnetic
moment of this system to be determined; at 4.2 K it is in the
range of 1.72mB.
For spherical particles the MöS data processing turned out to
be more complicated since these particles exhibit a typical
superparamagnetic spectrum at room temperature. It can indeed
be expected that the strong reduction of the lattice parameter in
very small particles [1] will enhance the distortion (oxygen
parameter) in the spinel structure. Moreover, the energetically
most favorable spherical shape in such small particles may also
introduce strong deviations from the ideal lattice positions.
However, at 80 K the particles’ spectra reveal the co-existence
of both ferromagnetic and superparamagnetic phases. The
temperature dispersion of the spectrum is presented in Fig. 4. It
shows that the particles have superparamagnetic properties at
room temperature. The cation distribution of these particles was
also studied by MöS at 4.2 K and external magnetic field of 5 T
(Fig. 5).
Cu0:43 2þ Fe0:57 3þ ½Fe1:43 3þ Cu0:57 2þ O4
This distribution yields a considerably higher elementary
magnetic moment (in the range of 4.44mB). This is in a good
agreement with the increase observed of the saturation
magnetization Ms of spherical particles (Table 3).
The results obtained lead to the conclusion that there is a
gradient of the crystallization in the short-range order in the
spherical particles which is connected with the cavity size in the
A and B sublattices. The migration of Cu2+ cations from the
core to the surface is influenced by that gradient. The octahedral
cavities having higher symmetry are built with priority and their
structure is closer to that of a bulk material and, respectively, to
the edged particles.
Table 2
Hyperfine parameters extracted from MöS spectra of sample CuFe2-SQ with
edged particles
Sample Site Hhf 2e dFe Relative
(T) (mm/s) (mm/s) area (%)
CuFe2-SC A 47.9 0.00 0.24 46
B 50.7 0.37 0.36 54
 I. Nedkov et al. / Applied Surface Science 253 (2006) 2589–2596
Fig. 4. Evolution of Mössbauer spectra of CuFe2O4 nanoparticles with size 6  2 nm—sample CuFe1-Sp at (a) room temperature and (b) 80 K.
This effect has been discussed [1] and it was shown that in
the case of spherical magnetite particles the Laplace pressure
leads to changes in the tetrahedral and octahedral cavity
volumes which creates different filling in comparison to that of
the bulk structure. The increase of the A-sublattice radius
caused by Laplace pressure results in a lower crystal symmetry
and decreased crystal energy.
A VSM model 8810 ADE Techn. Inc. was used to study the
magnetic properties of samples 1-Sp and 2-SC at 4.2 K and
magnetic field up to 3 T. The results are presented in Table 3.
The saturation magnetization (Ms) for sample CuFe2-SC
(larger particles) is slightly lower in comparison to that of bulk
copper ferrospinel, which could be explained by the nanosized
state. However, for spherical particles (CuFe1-Sp) Ms is higher
than that of the bulk material and this is not typical for the
nanosized state [2]. The cation distribution in the two
sublattices can be expressed by Boltzmann equation:
x(1  x)/(1  x)2 = eE/kT, where x is the number of Cu2+
cations passing from octahedral to tetrahedral sites. The cation
re-distribution in the sublattices in spherical nanosized
particles is accompanied by changes in the magnetic moment,
as it could be expected from the theory of the non-compensated
antiferromagnetism. To interpret the magnetic properties of
both types of samples, we considered frozen magnetic
moments and ignored the temperature influence. Our
considerations were based mainly on the crystalline field
energy, E.
Fig. 5. Evolution of Mössbauer spectra of CuFe2O4 nanoparticles with size
6  2 nm—sample CuFe1-Sp at 4.2 K in external magnetic field 5 T.
2593
Although both types of samples are single-phase and have
the same stoichiometry, the XRD pattern of the larger particles
showed the presence of co-operative Jahn–Teller effect which
was obvious for the spherical particles with very small size [11]
where the XPS data proved tetrahedral deviation in the surface
layer. On the other hand, a comparison between the XPS and
MöS data gives us reason to claim that the crystal surface and
the core exhibit different distortion. The experimental data
showed that the two types of particles have different magnetic
properties defined by the difference in the magnetocrystalline
structure of the shell and the core.
The JT effect exists in crystals containing transitional metal
ions, whose ground orbital state is degenerated so that a
spontaneous degeneration of the orbits of neighboring ions can
arise. It leads to lowering of the crystal field symmetry and a
minimum of system energy. In the case of spherical crystal
symmetry, the state of ions with configuration d9(Cu2+) is a
transitional state between d10 and d7 (low spin in case of a
strong crystal field). For octahedral coordination the external
electron belongs to configurations d6e d1g , and can occupy one of
the orbits d2x d2y , d2z . Orbits de and dg are exchanged when the
cations are in tetrahedral coordination. In both cases the result
is tetrahedral degeneration, lower crystal symmetry and
different crystal cell parameters. For bulk copper ferrospinel
with octahedral JT distortion c/a > 1, while for CuCr2O4 with
tetrahedral distortion c/a < 1 and the changed crystalline
anisotropy leads to different magnetic properties [3].
For copper ferrospinel at room temperature, the value of K1
is negative (K1 = 0.6.105 J/m3) and the easy magnetization
axis coincides with the spatial diagonal h0 1 0i of the
elementary cube. The spin–orbital interactions in a Cu–ferrite
with tetragonal crystal lattice distortion due to co-operative
Jahn–Teller effect predominate in the appearance of magneto-
crystalline anisotropy. The best interpretation of the energy
spectrum of such systems is offered by the single-ion theory,
whereby the physical nature of the uniaxial anisotropy can be
represented by the Hamiltonian of the spin–orbital interactions:
Ĥ ¼ V ex þ V LS ¼ 2mB H ex S þ lLS (1)
In a low-symmetry field caused by the Jahn–Teller effect the
orbital moment, L, and the spin moment, S, are not zero. In such
2594 I. Nedkov et al. / Applied Surface Science 253 (2006) 2589–2596
Table 3
Saturation magnetization (Ms) per gram of samples and effective anisotropy (Hc) calculated from M(H) curve of the samples measured at 4.2 K
Sample Particle’s dimensions Ms (emu/g)
(L/D nm or D, nm)
Edged particles SC 1300  20/200  20 32
Spherical particles 6+2 35.6
a case, the potential energy of the electrons in the crystalline
field, VLS plays an important role in the energy levels splitting
and the relatively small distance between the cations depends
strongly on the orientation of the exchange interaction field,
Hex. In favorable conditions this may cause strong magneto-
crystalline anisotropy. One should expect this effect to be
substantial in the edged (SC) particles, where the JT effect is
clearly expressed. The data yielded by the XPS and MöS
analyses for spherical nanosized particles led us to the assump-
tion for the existence of a Jahn–Teller effect gradient—from the
B-sublattice on the surface to a compensation of the tetragonal
distortion in the two sublattices in the core (Fig. 6). Inasmuch as
the atoms’ energy spectrum in the crystalline field depends on
the Hex orientation, which determines the orientation of the spin
magnetic moments with respect to the crystalline axes x, y and z
in the complicated crystalline structure picture, as revealed by
the structural studies, we may assume the existence in the
nanoparticle of an effective exchange interaction field Heff.
Fig. 6. Canting angle and hyperfine field distribution in both sublattices –
tetrahedral (A) and octahedral (B) of CuFe2O4 nanostructured spherical particle
– sample CuFe1-Sp with diameter 6  2 nm.
Hc (mT) Keff (erg/cm3) (for bulk tetragonal
CuFe2O4, K1 = 0.6  105 J/m3)
39 0.62  105 J/m3
41 0.72  105 J/m3
The spin–orbital interaction, Eq. (1) is one of the main
reasons for the appearance of magneto-crystalline anisotropy in
the oxide crystal. In ferroxide materials, the crystal’s total
magnetic moment has a spin origin and its energy depends on
magnetization vector orientation with respect to the crystal-
lographic axes and is determined by the spin–orbital interac-
tion, since the ions’ orbital magnetic moment is directly related
to the crystal lattice. If one assumes that the atomic magnetic
moments are localized in the crystal lattice sites and are
oriented in parallel, the magnetic dipole interaction contribu-
tion will depend on the orientation of the total magnetic
moment M with respect to the crystallographic axes. The
solution of Landau–Lifshitz equation for Larmor-type motion
for a volume with magnetization will yield:
1 @M
¼ ½MH eff  (2)
g @t
From phenomenological considerations, the energy of the
magneto-crystal anisotropy as a function of the cosines (a) of
the magnetization
P vector with respect to the crystal axes is
Ea ¼ n K n a2n , where Kn is the constant of crystal anisotropy,
to be determined experimentally; for a cubic crystal (anisotropy
constant K1) with a magnetic field applied at an angle u with
respect to the easy magnetization axis h0 1 0i one will have
a1 = 0, a2 = cos u, a3 = sin u. The energy of magneto-crystal-
line anisotropy of such a particle is described by:
K1
Emc ¼ K 1 sin2 u cos u ¼ sin2 2u (3)
4
On the other hand, the shape of the edged (SC) particles can
be approximated by an ellipsoid (see Fig. 1). For such a particle
one should expect anisotropic behavior under the application of
an external magnetic field parallel to the c axis for K1 > 0, and
perpendicular to it for K1 < 0. Maxwell’s theory stipulates that
uncompensated charges will arise on the poles of such a
particle, which will lead to magnetic energy dissipation; i.e.,
shape anisotropy will exist, with the energy density depending
on DN = N?  Nk; the shape anisotropy energy can then be
written as:
K1
Esh ¼ sin2 2u þ 0:5m0 ðN ?  N k ÞMs2 sin2 u
4
K1
¼ sin2 2u þ K sh Ms2 sin 2u (4)
4
Shape anisotropy’s contribution is present in edged particles
and Eq. (4) describes in practice its energy of anisotropy. In
spherical particles the contribution of the shape anisotropy is
low, so that these particles’ magnetocrystalline anisotropy is
described by Eq. (3). The fact that in the core of a spherical
 I. Nedkov et al. / Applied Surface Science 253 (2006) 2589–2596
particle one sees a transition from a tetragonal distortion in
octahedral surrounding to a distortion in both sublattices can
hardly be considered as a two-phase magnetic state of the
system; one should rather speak of sub-structures in the
particle’s core with changed crystal symmetry with Eq. (3)
describing the energy of the entire system, but K1SC 6¼ K1Sp .
In nanosized particles there exists another type of anisotropy
that has to do with surface state of the magnetic moments. The
energy of interaction between two magnetic ions in a crystal
(magnetic moment m) is a function of the angle u between the
vector of spontaneous magnetization and the line connecting
the two ions and depends on the distance, r; assuming magnetic
dipole interaction, this energy is (3m2/r2). For ions on the
surface, Néel [23] introduced a pseudo-dipole term, l, which,
besides the spin–orbital interaction, accounts for the interaction
between two adjacent ions, so that he arrived at Ea = ((3m2/
r3) + l)(cos2 u  (1/3)). In a cubic crystal, the value of cos2 u
averaged by summation over close neighbors is 1/3, which
means that the term (3m2/r2) does not exist in the expression
for the average value of the anisotropy energy of the core; this
condition is violated when the ion is located on the surface. In
long-range order, this interaction can be considered as
demagnetizing.
The pseudo-dipole interaction between surface ions leads to
the appearance of energy of surface anisotropy, which can be
expressed as:
Esurf ¼ K surf cos2 u (5)
where Ksurf is the constant of surface anisotropy density and u is
the angle between easy magnetization axis and the normal to
the surface. This type of anisotropy should be present in both
types of particles.
From a magnetic point of view, the surface of a spherical
nanoparticle is formed by ions with uncompensated magnetic
moments; a surface layer thus exists, which, in contrast with the
antiferromagnetic structure in the core, has an unordered spin-
magnetic structure [23]. The MöS and XPS analyses data give
us grounds to maintain that, besides the unordered magnetic
structure caused by the ‘‘boundary effect’’, this surface layer
exhibits also a magnetocrystalline structure different from that
in the particle’s core. In the spherical nanosized particles
studied here, the relative volume of this layer with respect to the
total volume may be substantial, which may bring about
magnetic exchange interactions [24]. The energy of such
exchange anisotropy between the spin-unordered surface and
the ordered core is usually described as:
Eex ¼ K ex cos u (6)
Bearing in mind the above considerations, it is clear that in
both types of nanosized particles studied the experimentally
obtained anisotropy coefficients (Table 3) represent compre-
hensive quantities that reflect the specificity of a number of
different magnetic interactions where the direction (u) of the
magnetization vector with respect to an external magnetic field
may be different; one should, therefore, refer to an effective
coefficient of anisotropy where the contribution of the different
2595
magnetic interactions is different in the edged and in the
spherical nanosized particles.
In edged particles; K eff ¼ K1SC þ K sh þ K surf
In spherical particles; K eff ¼ K1Sp þ K ex þ K surf
Our earlier studies of magnetite (a model system for
ferrospinels) by means of low-energy MöS demonstrated [24]
that the thickness of the layer where structural changes and an
unordered magnetic structure are possible is in the order of
3 nm. In the case of a spherical particle with maximal diameter
up to 8 nm, the magnetically ordered crystal lattice occupies
about 25% of the total volume, while for the larger edged
particle this value is approximately 97%. Thus, the larger
deviations in Keff for the smaller particles are due to the larger
relative contribution of the surface and exchange anisotropy.
4. Conclusions
The MöS and XPS studies showed that, in nanosized
spherical particles containing Jahn–Teller ions, the tendency
for a lower particle energy leads to the lower symmetry
propagating in both ferrospinel sublattice. This results in a
cation distribution that is not typical for edged particles and for
the bulk single crystal. We suggest that the changes occur
gradually—from the surface, where one observes tetragonal
distortion in octahedral sites only, to the core, where distortion
also exists in tetrahedral sites. This reflects on the spin–orbital
interactions in the crystal cell, respectively, on the magneto-
crystalline anisotropy and on the formation of the system’s total
magnetic moment, which for a spherical particle may prove to
be different from that of edged particles or bulk crystal, the
identical stoichiometry notwithstanding.
The surface XPS analysis did not reveal the presence of
single-valence copper; i.e., no reduction of copper and oxidation
of iron have taken place, as is typical for the surface layer of
magnetite and some other ferrospinels after heat treatment.
With nanosized particles one deals with the interplay of
several factors affecting the magnetocrystalline anisotropy, the
latter thus having a complex nature; the value of the anisotropy
coefficient, as an experimentally obtained parameter, must,
therefore, be considered an effective value reflecting the
influence of the individual factors on the magnetic anisotropy.
Acknowledgments
This work has been supported by Bulgarian National Found
Project HT-1/01/03, F.W.O., Flanders, Belgium and CNRS,
France.
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