Dipolar effects on the magnetic phases of

superparamagnetic clusters
Cite as: J. Appl. Phys. 123, 233902 (2018); https://doi.org/10.1063/1.5030739
Submitted: 25 March 2018 . Accepted: 31 May 2018 . Published Online: 19 June 2018

S. S. Pedrosa, S. M. S. B. Martins, R. M. Souza, J. T. S. Dantas, C. M. Souza, G. O. G. Rebouças, J. M. de

Araújo, Ana L. Dantas , and A. S. Carriço

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© 2018 Author(s).
 JOURNAL OF APPLIED PHYSICS 123, 233902 (2018)

Dipolar effects on the magnetic phases of superparamagnetic clusters

S. S. Pedrosa,1 S. M. S. B. Martins, Jr.,1 R. M. Souza,1 J. T. S. Dantas,1 C. M. Souza,1
G. O. G. Rebouças,2 J. M. de Araujo,1 Ana L. Dantas,3 and A. S. Carriço1
1
Department of Physics, UFRN, 59072-970 Natal, RN, Brazil
2
Department of Physics, UFERSA, 59515-000 Angicos, RN, Brazil
3
Department of Science and Technology, UERN, 59104-200 Natal, RN, Brazil
(Received 25 March 2018; accepted 31 May 2018; published online 19 June 2018)
We report a theoretical study of the impact of dipolar interactions on the room temperature
magnetic phases of superparamagnetic nanoparticles confined in spherical and ellipsoidal clusters.
We consider Fe3O4 nanoparticles with size ranging from 9 nm to 12 nm, arranged with uniform
density in hundred nanometer-sized clusters. We show that one may have a large enhancement of
the initial susceptibility for ellipsoidal clusters of high eccentricity, as required for most biomedical
applications. Spherical clusters display a reduction of the initial susceptibility, due to the early
nucleation of new magnetic phases. In densely packed systems, the dipolar interaction may lead to
thermal stabilization of the individual nanoparticle moments, while keeping the cluster superpara-
magnetic, with a vanishingly small magnetic moment in the absence of an external field. The
theoretical model is used to discuss recent findings on quasi-one-dimensional arrays of superparamag-
netic Fe and Co nanoparticles, and on spherical clusters of superparamagnetic Fe3O4 nanoparticles.
Published by AIP Publishing. https://doi.org/10.1063/1.5030739

I. INTRODUCTION orientation,31,32 revealed that the dipolar interaction may

A large deal of research effort has recently been
focused on the study of magnetic phases of clusters of
superparamagnetic nanoparticles. The interest stems from
both purely fundamental reasons as well as the promising
chances of designing optimized magnetic systems for bio-
medical applications.1–8
A high concentration of nanoparticles may lead to novel
effects. The nanoparticles may turn to be coupled together
and exhibit collective behavior.9,10 This may lead to super-
ferromagnetism, with a nonzero remanent magnetic moment
and coercive field for temperatures above the nanoparticles’
blocking temperature. Most commonly, superferromagnet-
ism originates in the dipolar interaction.11,12 It may also arise
from the close contact between nanoparticles. The exchange
interaction between surface atoms of two magnetically
ordered nanoparticles can also result in significant interac-
tion effects that affect the thermal relaxation.4,13,14
Optimization of nanoparticle clusters for biomedical
applications requires high magnetic susceptibility, allowing
better targeting efficiency,15–17 larger cellular uptake,18,19
improved magnetic resonance contrast,20,21 and larger effi-
ciency for magnetic hyperthermia.22 Ideally, the cluster must
have vanishingly small magnetic moment in the absence of
external fields to prevent agglomeration induced by the mag-
netic interaction between clusters.
Theoretical predictions indicate that the dipolar interac-
tion energy may lead to dipolar ferromagnetism,23,24 vortex-
like states,25 and spin flop-like states.26
Dipolar ferromagnetism has been reported in experimen-
tal studies of nanoparticle systems with no preferential crystal-
lographic orientation.27–32 Interestingly, previous studies
on quasi-one-dimensional arrays of superparamagnetic Fe
and Co nanoparticles, with no preferential crystallographic
either enhance the initial magnetic susceptibility, preserving
the superparamagnetic character of the nanoparticles, or stabi-
lize the ferromagnetic order.
In addition, reports on spherical agglomerates of super-
paramagnetic nanoparticles33,34 indicate that clustering may
lead to relevant reduction of the initial susceptibility.
These experimental reports indicate that regardless of
the values of the anisotropy energy, the interparticle dipolar
interaction may change the intrinsic thermal relaxation prop-
erties of the individual nanoparticles.
Furthermore, the topological restriction on the nanopar-
ticle arrangements is a key issue. This is not surprising since
the dipolar interaction is long-ranged and anisotropic. Thus,
the impact of the dipolar interaction on the cluster magnetic
phases is likely to be strongly affected by the global nanopar-
ticle positioning within the cluster.
We presently discuss the impact of the dipolar interaction
on the room temperature magnetic phases and the low field
susceptibility of Fe3O4 superparamagnetic nanoparticles, with
the diameter ranging from 9 nm to 12 nm, distributed with uni-
form packing densities in spherical and ellipsoidal clusters.
Spherical clusters and ellipsoidal clusters with eccentric-
ities of 0.7, 0.9, and 0.97 are discussed to identify the impact
of the eccentricity in the dipolar effects on the magnetic
phases and low field susceptibilities.
We have seen that above a critical density of nanopar-
ticles, ellipsoidal clusters may exhibit remanence and coer-
civity. At the critical density, there is a transition from the
superparamagnetic state to the superferromagnetic state.4
The critical density for dipolar superferromagnetism is
largely dependent on the cluster topological layout and the
nanoparticle diameters. For each case in this study, we have
numerically checked the lowest value of the nanoparticle

0021-8979/2018/123(23)/233902/13/$30.00 123, 233902-1 Published by AIP Publishing.

233902-2 Pedrosa et al. J. Appl. Phys. 123, 233902 (2018)

density for which the cluster remains superparamagnetic, as values of the magnetization parameters41 for Fe3O4
the nanoparticles originally were. (M ¼ 510 emu/cm3) and Fe (M ¼ 1714 emu/cm3).
We have found that the cluster magnetic phases and the The present theoretical model extends the basic setup of
initial susceptibility may be tailored by the values of the the micromagnetic theory, by including thermal effects in a
eccentricity, the nanoparticle diameter, and the packing self-consistent manner.
density. The superparamagnetic Fe3O4 nanoparticles were posi-
For spherical clusters, regardless of the nanoparticles tioned at the sites of simple cubic lattices and the strength of
diameter, clustering leads to a reduction of the initial suscep- dipolar effects was controlled by choosing the value of the
tibility, as compared to the isolated particle value. We have lattice parameter. Each nanoparticle is supposed to be small
also found that ellipsoidal clusters may be tailored to have enough to have uniform magnetization and is represented as
susceptibility enhancement by an order of magnitude. a point dipole, irrespective of its geometrical shape.
In addition, at remanence, the nanoparticle cluster mag- This choice allows a simpler first view, especially for
netic phases have a unique property. The dipolar energy comparison with the experimental results. Similar results
leads to thermal stabilization of the individual nanoparticle should come out with the nanoparticles positioned in higher
moments. Large nanoparticle densities may allow a nearly packing densities lattices, such as the hexagonal close packed
full thermal value of the nanoparticle magnetic moments. structure, for appropriate values of the lattice parameter. The
Despite this, the nanoparticle cluster is superparamagnetic, dipolar sums extend over a large number of nanoparticles,
with a rather small magnetic moment, as required for bio- not only the immediate neighborhood of a given nanoparticle.
medical safety. Thus, the dipolar field acting on each individual nanoparticle
may turn to be largely determined by the size and the topo-
II. THEORETICAL MODEL logical layout of the cluster, and not by its immediate neigh-
borhood or the nanoparticle geometrical shape.
We consider N superparamagnetic nanoparticles confined Our main assumption is that the magnetic phases of the
in ellipsoidal and spherical clusters with uniform density. The nanoparticles clusters are controlled by the dipolar interac-
nanoparticles are located on the sites of simple cubic lattices, tion between the nanoparticles. We have neglected contribu-
and the lattice parameter is adjusted to set the nanoparticle tions from the nanoparticles’ anisotropy energy. Therefore,
packing density. we assume that the thermal average value of each nanoparti-
The cluster magnetic phases are found using local-field cle moment may be calculated using a Langevin function.
algorithms which allow calculating the orientations and the Thus, we assume that each individual nanoparticle is isotro-
thermal average values of the nanoparticle magnetic pic and may be magnetized in any direction. This choice
moments (h~ l j i; j ¼ 1; …; N) in a self-consistent manner. allows a self-adjustment of the clusters magnetic phases, and
Extending previous results,35–40 we presently investigate the the thermal values of the magnetic moments of the individ-
thermal stabilization of dipolar phases, in a system of super- ual nanoparticles, to the requirements imposed by the dipolar
paramagnetic nanoparticles. The nanoparticle moment orien- interaction.
tations and thermal average values are adjusted self- A simple estimative of the relative strength of the
consistently to incorporate the features associated with the dipolar and anisotropy fields may be made comparing the
long-ranged and anisotropic nature of the dipolar interaction. dipolar and anisotropy energies. A 9 nm diameter Fe3O4
The effective local field at each nanoparticle is obtained holds a magnetic moment of l ¼ 2.1  104 lB at saturation.
from the magnetic energy, H ~eff
j ¼
@E
, and the thermal Therefore, the strength of the dipolar energy coupling two
lj
@~
nanoparticles of diameter d in contact and positioned along
average values are calculatedusing a Langevin average for
the magnetization is Ed ¼ 2l2 =d 3 and amounts to a tempera-
l0 Hjeff ture of 768 K. The anisotropy energy strength is Ea ¼ KV,
l j i ¼ l0 L
each nanoparticle, h~ kB T ^ j , where l0 is the sat-
l
where K and V are the uniaxial anisotropy energy density
uration value of the nanoparticle magnetic moment. and the nanoparticle volume. Ed is twice larger than the
The equilibrium configuration is found by adjusting anisotropy energy. We note that summing the dipolar energy
self-consistently the nanoparticle moments’ directions and over all nanoparticles, we may find a further enhancement of
thermal values to having each nanoparticle moment aligned the dipolar energy.
with the effective local field, so that the magnetic torque is The validity of the theoretical model has been demon-
lji  H
zero (h~ ~eff
j ¼ 0; j ¼ 1; ::; N). Convergence is checked strated by reproducing the main features of experimental
to ensure that the magnetic torque is smaller than 10–29 J. results reporting dipolar effects on Fe and Co linear chains,31,32
The magnetic energy is given by and spherical clusters of Fe3O4 superparamagnetic nanopar-
! ticles.33,34 In addition, the theoretical model reproduces previ-
X 1XX ~ l k 3ð~
l j :~ ~jk Þð~
l j :R ~jk Þ
l k :R
E¼ ~
H:~lj þ  ; ous theoretical results, the vortex-like states25 and spin flop-
j
2 j k R3jk R5jk like states,26 which were predicted for dipolar interacting sys-
(1) tems of point dipoles in simple cubic lattices.
The study of the impact of the dipolar interaction on the
where the first term is the Zeeman energy and in the dipolar magnetic phases and the thermal relaxation properties of
energy term, the vector R ~jk is the relative position of the superparamagnetic nanoparticles confined in clusters with a
nanoparticle moments ~ l j and ~ l k .We have used the bulk large number of nanoparticles is a theoretical challenge.
233902-3 Pedrosa et al.
Using, for instance, the Monte Carlo technique, one
should be able to represent the superparamagnetic nature of
each nanoparticle and yet, allow the dipolar interaction
between all nanoparticles to interfere in the intrinsic thermal
relaxation process of individual nanoparticles.
Setting up a theoretical model, using the Monte Carlo
technique, to investigate the room temperature properties
of hundreds of nanometer-sized spherical clusters, with
thousands of superparamagnetic nanoparticles, in terms of
the individual nanoparticles, thermal average magnetic
moments, becomes prohibitively time-consuming.
Approximations have been used42–44 in order to over-
come the Monte Carlo method system size restrictions and
study either the impact of the long ranged dipolar interaction
for the investigation of the magnetic phases of systems of a
large number of small ferromagnetic nanoparticles, or the
competition between the exchange and dipolar energies on
the magnetic phases of a single ferromagnetic nanoparticle
of sub-100 nm size.
The fast Monte Carlo method previously proposed42 to
study the magnetic phases of a single ferromagnetic nanopar-
ticle of sub-100 nm size, with a few million magnetic
moments, combines the standard Monte Carlo and scaling
techniques to reduce the actual system size and the number
of inter-dependent magnetic variables. We note that in this
case, the predictions of the micromagnetic theory45 have
been reproduced and used as a check to validate the fast
Monte Carlo method results.
III. RESULTS AND DISCUSSIONS
For ellipsoidal clusters, we have chosen the large axis
along the x–axis direction and examined the magnetic phases
starting with the nanoparticle clusters saturated by an exter-
nal field applied along the large axis direction. An external
field strength of 4 kOe suffices to saturate all the clusters
investigated. For all systems investigated, the magnetization
vanishes at remanence.
We start the calculation at large external field values,
and proceed to remanence by reducing the external field
strength, using a fine external field grid, with steps of the
order of 2 Oe.
At large external field values, the nanoparticle moments
are initialized with full thermal average values, making small
angles with the external field direction. The self-consistent
equations are then used to find the equilibrium phase. For
each subsequent value of the external field, the self-
consistent procedure is initialized with the magnetic state
corresponding to the equilibrium state of the previous value
of the external field. The nanoparticles’ magnetic moment
directions and thermal values are then adjusted to meet the
new equilibrium conditions.
Before the discussion of the magnetic phases of spheri-
cal clusters and ellipsoidal clusters with small and large
eccentricities, it is instructive to describe the Vortical State
(VS) and the Dipolar Spin Flop State (DSFS).
The vortical state has been predicted by Belobrov and
collaborators25 for a system of point dipoles on simple cubic
lattices. Belobrov’s model does not include thermal effects.
J. Appl. Phys. 123, 233902 (2018)
Each lattice point contains a freely rotating stable magnetic
or electric dipole.
A dipolar spin flop-like phase transition has been pre-
dicted by Galkin and Ivanov for a two-dimensional array of
nearly isotropic magnetic dipoles in a square lattice.26 The
spin flop-like phase is a two-sublattice pattern analogous to
the spin flop phase of weakly anisotropic Heisenberg
antiferromagnets.
We have extended Belobrov’s and Ivanov’s results and
have shown that the vortical state and a dipolar spin flop
state may form in a system of superparamagnetic nanopar-
ticles, confined in spherical and ellipsoidal volumes.
Throughout the paper, we show the Fe3O4 nanoparticles’
magnetic moment patterns, and the dipolar field patterns in
the clusters z ¼ 0 layer. The out-of-plane angle (h) is the
angle with the z–axis, and / is the angle with the x–axis.
Figure 1 illustrates the magnetic patterns of the DSFS
and the VS for a 228.6 nm diameter spherical cluster of 9 nm
diameter Fe3O4 arranged uniformly, densely packed with a
center-to-center distance of 10.98 nm.
The DSFS [Fig. 1(a)] forms for an external field strength
of 0.17 kOe. The VS [Fig. 1(c)] is the magnetic pattern at
remanence. For both the DSFS and the VS, except for
the near-surface region, the magnetic pattern corresponds to
four sublattices, as shown in Fig. 1(b) for the DSFS, and in
Fig. 1(d) for the VS. The values of the out-of-plane angle (h)
and the angle with the external field direction (/) are shown
in Table I.
The DSFS comprises lines along the x–axis direction
with the orientation of the moments with the external field
resembling that of the spin flop state of two-sublattice uniax-
ial antiferromagnets. Consecutive nanoparticle moments
alternate the orientation with the external field (/ ¼ 658 ).
Lines of moments along the y–axis have the projection in the
xy–plane in the same direction, resembling a ferromagnetic
pattern. However the out-of-plane angles of consecutive
nanoparticles alternate (h ¼ 642 ), in a manner which
resembles the spin flop state of two-sublattice uniaxial anti-
ferromagnets. Consecutive layers of nanoparticles, along the
FIG. 1. (a) The Dipolar Spin Flop State (DSFS) and (c) the Vortical State
(VS) for a 228.6 nm diameter spherical cluster of 9 nm diameter Fe3O4 nano-
particles arranged uniformly, with a center-to-center distance of 10.98 nm.
Figures (a) [and (c)] show the Fe3O4 nanoparticles magnetic moment pat-
terns in the z ¼ 0 layer of the DSFS, for an external field strength of
0.17 kOe along the x–axis, (and the VS in remanence). The color barcode
indicates the out-of-plane angle (h) and the arrows mark the two values of h
for the DSFS and the VS. Figures (b) [and (d)] show the 4-sublattices com-
posing the magnetic structure of the DSFS (and VS), as described in detail
in Table I.
233902-4 Pedrosa et al.
TABLE I. Polar (h) and azimuthal (/) angles of the four sublattices of the
Dipolar Spin Flop State (DSFS) and the Vortical State (VS) of a 228.6 nm
diameter spherical cluster of 9 nm diameter Fe3O4 nanoparticles distributed
uniformly, with a center-to-center distance of 10.98 nm. The values of the
external field strength along the x–axis and the thermal average value of
magnetization are also shown.
DSFS VS
H ¼ 0.17 kOe H ¼ 0.00 kOe
hM=Ms i ¼ 0:54 hM=Ms i ¼ 0:54
H (deg) / (deg) h (deg) / (deg)
1(red) 48 þ58 52 þ50
2(gray) 132 þ58 128 þ130
3(green) 48 58 52 130
4(blue) 132 58 128 50
z–axis direction, display similar magnetic patterns with small
changes in the out-of-plane angles, with the consecutive
y–axis lines of nanoparticle magnetic moments alternating
the orientation with the x–axis.
The VS consists of an arrangement of the nanoparticle
magnetic moments resembling the vortex state of ferromag-
netic materials. In Fig. 1(c), the moments are in closed loops,
with clock-wise chirality, with alternating out-of-plane angle
(638 ). Consecutive layers of nanoparticles, along the
z–axis direction, display similar magnetic patterns with small
changes in the out-of-plane angles, and alternating chirality.
We have seen that the DSFS, VS, and an antiferromag-
netic state (AFS) are the main features of the magnetic
phases along the magnetization curves. The AFS consist of
nanoparticles arranged ferromagnetically in lines along the
x–axis, with the magnetic moments of neighboring lines
pointing in opposite directions. Throughout the paper, we
show the magnetic phases and dipolar field maps, using the
z ¼ 0 layer of nanoparticles.
We anticipate a brief description of the origin of the
large differences in susceptibility of ellipsoidal clusters and
spherical clusters.
Reducing the external field strength from the saturation
value, we have found that large eccentricity ellipsoidal clus-
ters stay saturated down to small external field values. Large
changes in the magnetization occur at external fields of the
order of a few Oersted, leading to large susceptibility values.
For spherical clusters, the departure from saturation is
seen for larger external field values. The magnetic phases
change gradually, with the magnetization dropping from sat-
uration to vanishingly small values at remanence. The mag-
netization changes in an external field interval of the order of
a few hundred Oe, leading to susceptibilities smaller than the
isolated single nanoparticle values.
The differences between the sequence of magnetic
phases exhibited by ellipsoidal clusters and spherical clus-
ters, from saturation to remanence, originate in the intrinsic
anisotropy of the dipolar interaction. A preliminary estima-
tive of the impact of the anisotropy of the dipolar interaction
on the clusters magnetic phases can be made using a simple
argument.
Consider a pair of nanoparticles with parallel magnetic
moments (~ l j ), with relative position given by ~
l i ) and (~ r,
J. Appl. Phys. 123, 233902 (2018)
making an angle (hij) with the magnetic moments. The dipo-
lar energy interaction is given by
li lj  
Edip ¼  3
3 cos2 hij  1 : (2)
r
The dipolar interaction favors ferromagnetic order for
hij  54:75 , or antiferromagnetic coupling otherwise.
The central nanoparticle in a 228.6 nm long axis ellip-
soidal cluster with an eccentricity of 0.97, containing 289
nanoparticles, is surrounded by 288 nanoparticles out of
which 82% are dipolar coupled ferromagnetically to the cen-
tral nanoparticle. This fraction drops to 54% for a 228.6 nm
long axis ellipsoidal cluster with an eccentricity of 0.7, con-
taining 2477 nanoparticles, and to only 44% for a 228.6 nm
diameter spherical cluster with 4945 nanoparticles.
Large eccentricity ellipsoidal clusters have a good frac-
tion of the nanoparticles close to the long axis. At saturation,
these nanoparticles are subjected to a dipolar field which
comes mostly from other nanoparticles positioned near the
long axis. As a result, the dipolar field is parallel to the nano-
particle moments.
At saturation, the thermal stabilization of each nanopar-
ticle magnetic moment is largely due to the external field. By
reducing the external field value, a large fraction of the local
field originates from the dipolar field, which points in the
external field direction. From saturation, down to remanence,
there is a gradual transfer of weight from the external field to
the dipolar field in the composition of the local field at each
nanoparticle. This allows the thermal stabilization of the uni-
form state down to rather small external field values.
Spherical clusters have quite different layouts of nano-
particle relative positions. At saturation, with all nanoparticle
moments pointing along the external field direction, compara-
ble fractions of the dipolar energy favor the global ferromag-
netic arrangement and the antiferromagnetic arrangement. As
a result, even for external field values of the order of a few
hundred Oe, the ferromagnetic order gives way to new mag-
netic phases controlled by the dipolar interaction. There is a
continuous decrease in the cluster magnetic moment, from
saturation to remanence, in a wide external field interval.
In Fig. 2, we show a global picture of the impact of the
eccentricity on the initial susceptibility, and the magnetic
phase at remanence, of 9 nm diameter Fe3O4 nanoparticle
clusters. The nanoparticles are distributed uniformly, with a
center-to-center distance of 10.98 nm, in a 228.6 nm diameter
spherical cluster, and a 228.6 nm long axis ellipsoidal cluster
with eccentricities of 0.7, 0.9, and 0.97. The nanoparticle
cluster initial susceptibility is shown in units of the initial sus-
ceptibility of an isolated 9 nm diameter Fe3O4 nanoparticle.
The spherical cluster displays a vortical state at rema-
nence, while the ellipsoidal clusters’ remanent phase is
strongly dependent on the value of the eccentricity. Large
eccentricity ellipsoidal clusters (e ¼ 0.9 and e ¼ 0.97) display
the AFS at remanence. For an eccentricity of 0.7, the remanent
phase combines the AFS at most of the cluster volume, with a
fraction of the nanoparticles near the poles in the vortical state.
One remarkable feature is the large thermal average
value of the individual nanoparticle moments at remanence.
233902-5 Pedrosa et al.
FIG. 2. Relative susceptibility of 9 nm diameter Fe3O4 nanoparticles distrib-
uted uniformly, with a center-to-center distance of 10.98 nm in ellipsoidal
clusters with eccentricity ranging from 0.0 to 0.97. In the insets, we show
the magnetic patterns at remanence of the Fe3O4 nanoparticles in the z ¼ 0
layer of (a) 228.6 nm diameter spherical cluster, and 228.6 nm long axis
ellipsoidal cluster with eccentricities of 0.7 (b); 0.9 (c); and 0.97 (d). The
top left barcode indicates the thermal average value of the Fe3O4 nanopar-
ticles’ magnetic moments, in units of the saturation value, and the right
barcode indicates the out-of-plane angle (h).
Except for a small fraction of the nanoparticles near the clus-
ter surface, the thermal average value of the nanoparticle
moments is 54% of the saturation value.
In addition, it is seen that the susceptibility of the spheri-
cal cluster is equal to the isolated nanoparticle susceptibility
(v0), while for the ellipsoidal cluster, the larger the suscepti-
bility the larger the eccentricity is, reaching a limit of v/v0
 16 for an eccentricity of 0.97.
We have found that the packing density, the eccentric-
ity, and the nanoparticle diameter have a large impact on the
value of the initial susceptibility and the magnetic phase at
remanence. A discussion of these issues is shown in Figs. 3
and 4.
FIG. 3. Susceptibility of ellipsoidal 9 nm diameter Fe3O4 nanoparticles clus-
ters of 0.97, 0.9, and 0.7 eccentricities, for values of the center-to-center dis-
tance ranging from 10.98 nm to 23.5 nm, and the long axis size ranging from
228.6 nm to 489.26 nm. The susceptibility is shown in units of the isolated
9 nm diameter Fe3O4 nanoparticle value.
J. Appl. Phys. 123, 233902 (2018)
FIG. 4. Susceptibility of spherical clusters of 9 nm, 10 nm, 11 nm, and 12 nm
diameter Fe3O4 nanoparticles, with the center-to-center distance ranging
from 9.9 nm to 26 nm, and diameter ranging from 207 nm to 540 nm. The
susceptibilities are shown in units of the corresponding isolated Fe3O4 nano-
particle values.
In Figs. 3 and 4, we show the impact of the center-to-
center nanoparticle distance (d) on the initial susceptibilities
of ellipsoidal and spherical clusters. Notice that increasing
the packing density leads to enhancement of the initial sus-
ceptibility of ellipsoidal clusters. For spherical clusters, the
opposite trend is seen. The susceptibility drops to values
smaller than the isolated nanoparticle susceptibility when the
packing density is large.
As shown in Fig. 3, for small packing density values,
the cluster susceptibility approaches the isolated nanoparticle
value. Also, the larger the susceptibility enhancement for
high packing density the larger the eccentricity is.
In Fig. 4, it is shown that increasing the packing density
of spherical clusters leads to susceptibility reduction. For all
chosen clusters, with Fe3O4 nanoparticle diameter ranging
from 9 nm to 12 nm, the susceptibility is smaller than that of
the isolated Fe3O4 nanoparticle.
For small packing densities, the cluster susceptibility is
equal to the isolated nanoparticle susceptibility. There is a
critical value of the center-to-center nanoparticle distance
(d*), below which the cluster susceptibility turns smaller
than the isolated Fe3O4 nanoparticle value.
There is a clear indication that the dipolar effects are
stronger for the 12 nm Fe3O4 nanoparticle cluster. d* 11 nm
for the 9 nm Fe3O4 nanoparticle cluster, with a center-to-cen-
ter nanoparticle distance only 22% larger than the nanoparti-
cle diameter. For the 12 nm Fe3O4 nanoparticle cluster, the
dipolar effect is stronger and the critical distance is larger. In
this case, d*  21 nm, corresponding to a center-to-center
nanoparticle distance equal to almost twice the nanoparticle
diameter.
In addition, for comparable values of the center-to-center
nanoparticle distance, relative to the nanoparticle diameter,
the dipolar effects are much larger in the 12 nm Fe3O4 nano-
particle cluster. For a center-to-center nanoparticle distance
10% larger than the nanoparticle diameter, the reductions of
233902-6 Pedrosa et al. J. Appl. Phys. 123, 233902 (2018)

susceptibilities are 75% for the 12 nm nanoparticle cluster,

and only 40% for the 9 nm nanoparticle cluster.
The sequence of magnetic phases from saturation to
remanence, for spherical or ellipsoidal clusters, contains
three stages. Starting at large external field (H) strengths in
the uniform state, at a critical value of the external field, the
DSFS is nucleated starting the magnetization reduction
towards remanence. At remanence, spherical clusters display
the VS, high eccentricity ellipsoidal clusters display the
AFS, and moderate eccentricity ellipsoidal clusters display
the AFS in most of the volume, with a small volume fraction
near the poles in the VS. The threshold external field value
for the nucleation of the DSFS is the key issue for controlling
the susceptibility.
In addition, we have found that there is a self-adjustment
of the nanoparticle magnetic moments with the local dipolar
field. Starting at the nucleation of the DSFS, by reducing the
external field strength, the individual nanoparticle magnetic
moments align progressively with the local dipolar field. The
gradual alignment with the dipolar field leads to enhancement
of the thermal average values of the nanoparticle magnetic
moments and the intensity of the dipolar field.
Figure 5 shows the magnetizations and susceptibilities
of ellipsoidal clusters of 9 nm Fe3O4 nanoparticles. The
details of the magnetic phases, from saturation to remanence,
showing the progressive alignment of the nanoparticle mag-
netic moments with the dipolar field, and the enhancement
of the magnetic moment thermal average values are shown
from Fig. 6 up to Fig. 12.
In Fig. 5, we show the magnetizations and susceptibilities
of 228.6 nm long axis ellipsoidal clusters of 9 nm diameter
Fe3O4 nanoparticles distributed uniformly, with a center-
to-center distance of 10.98 nm, with eccentricities of 0.97, 0.9,
and 0.7. Notice that relevant changes in the magnetization of
the 0.7 eccentricity cluster start at an external field strength of
0.3 kOe, while for 0.97 eccentricity, cluster magnetization FIG. 5. (i) Magnetization and (ii) relative susceptibility of 228.6 nm long
changes occur for a smaller value of the external field axis ellipsoidal clusters of 9 nm diameter Fe3O4 nanoparticles distributed
uniformly, with a center-to-center distance of 10.98 nm, with eccentricities
(0.092 kOe). of 0.97, 0.9 (left inset), and 0.7 (right inset). The magnetizations are shown
The uniform phase of the 0.97 eccentricity cluster is in units of the isolated nanoparticle saturation value and the susceptibilities
stable from saturation down to an external field strength of are shown in units of the isolated nanoparticles’ susceptibility.
0.092 kOe. The magnetization reduction in this external field
interval is due to thermal effects. As seen in Fig. 6, most of
the nanoparticles have a thermal average magnetic moment interval, leading to a smaller value of the cluster susceptibil-
around 41% of the saturation value. The dipolar field is paral- ity. Starting at H ¼ 0.3 kOe, a DSFS is nucleated at the cen-
lel to the nanoparticle magnetic moments, with a strength tral region, as shown in Fig. 10. The dipolar field strength is
around 0.19 kOe, which is larger than the external field value. smaller than the external field value and the magnetic
At an external field of H ¼ 0.088 kOe, the DSFS is moments are not aligned with the dipolar field. As the exter-
nucleated. As shown in Fig. 7, the DSFS is restricted to the nal field is reduced, the DSFS changes, favoring a progres-
cluster center, where the thermal values of the nanoparticle sive alignment of the magnetic moments with the dipolar
magnetic moments and the dipolar field strength are slightly field, and a small increase in the dipolar field strength and
larger than for H ¼ 0.092 kOe. By further reducing the exter- the magnetic moment thermal average values, as shown in
nal field strength, there is a further increase in the nanoparti- Figs. 11 and 12.
cle magnetic moment thermal values and dipolar field The stronger the dipolar effects are the larger the nano-
strength, as shown in Figs. 8 and 9, for H ¼ 0.068 kOe and particle diameter is. Figure 13 shows the magnetizations and
for H ¼ 0. The large susceptibility (v/v0  16) results from susceptibilities of spherical clusters with 10 nm, 11 nm, and
the gradual modification of the DSFS into the AFS in a rather 12 nm Fe3O4 nanoparticles, distributed uniformly with a cen-
small external field interval. ter-to-center distance 10% larger than the nanoparticle diam-
The 0.7 eccentricity ellipsoidal cluster exhibits a differ- eter, and of 390.7 nm long axis (eccentricity of 0.97)
ent sequence of magnetic phases, in a wider external field ellipsoidal clusters of 12 nm diameter Fe3O4 nanoparticles
233902-7 Pedrosa et al.
FIG. 6. (a.1) Magnetization and (a.2) dipolar field patterns of a 0.97 eccen-
tricity, 228.6 nm long axis ellipsoidal cluster of 9 nm diameter Fe3O4 nano-
particles distributed uniformly, with a center-to-center distance of 10.98 nm.
The panels correspond to an external field strength of 0.092 kOe (point (a) in
Fig. 5) and show the patterns at a z ¼ 0 layer of the Fe3O4 nanoparticles’
cluster. The left (right) color barcode show the thermal average values (out-
of-plane angles) of the nanoparticle magnetization (a.1) and the local dipolar
field (a.2).
distributed uniformly, with a center-to-center distance of
18.93 nm. The details of the magnetic phases, from satura-
tion to remanence, are shown from Fig. 14 up to Fig. 16.
The spherical cluster susceptibilities display flat pla-
teaus, corresponding to an almost linear magnetization drop,
starting at an external field value H*, where the dipolar
phases nucleate. The values of H* increase with the Fe3O4
FIG. 7. (b.1) Magnetization and (b.2) dipolar field patterns of a 0.97 eccen-
tricity, 228.6 nm long axis ellipsoidal cluster of 9 nm diameter Fe3O4 nano-
particles distributed uniformly, with a center-to-center distance of 10.98 nm.
The panels correspond to an external field strength of 0.088 kOe (point (b) in
Fig. 5) and show the patterns at a z ¼ 0 layer of the Fe3O4 nanoparticles clus-
ter. The left (right) color barcode show the thermal average values (out-of-
plane angles) of the nanoparticles’ magnetization (b.1) and the local dipolar
field (b.2).
J. Appl. Phys. 123, 233902 (2018)
FIG. 8. (c.1) Magnetization and (c.2) dipolar field patterns of a 0.97 eccen-
tricity, 228.6 nm long axis ellipsoidal cluster of 9 nm diameter Fe3O4 nano-
particles distributed uniformly, with a center-to-center distance of 10.98 nm.
The panels correspond to an external field strength of 0.068 kOe (point (c) in
Fig. 5) and show the patterns at a z ¼ 0 layer of the Fe3O4 nanoparticles’
cluster. The left (right) color barcode shows the thermal average values (out-
of-plane angles) of the nanoparticles’ magnetization (c.1) and the local dipo-
lar field (c.2).
nanoparticle diameters, from 0.37 kOe to 0.95 kOe, leading
to progressively smaller values of the cluster susceptibilities
(v/v0 ¼ 0.77, 0.43, and 0.25).
The susceptibility plateaus correspond to the nucleation
of the DSFS at H*, and the gradual changes in the DSFS
towards the VS at remanence, as shown in Figs. 14–16, for
the 12 nm diameter Fe3O4 nanoparticle spherical cluster.
FIG. 9. (d.1) Magnetization and (d.2) dipolar field patterns of a 0.97 eccen-
tricity, 228.6 nm long axis ellipsoidal cluster of 9 nm diameter Fe3O4 nano-
particles distributed uniformly, with a center-to-center distance of 10.98 nm.
The panels correspond to the patterns at remanence (point (d) in Fig. 5) and
show the patterns at a z ¼ 0 layer of the Fe3O4 nanoparticles’ cluster. The
left (right) color barcode shows the thermal average values (out-of-plane
angles) of the nanoparticles’ magnetization (d.1) and the local dipolar field
(d.2).
233902-8 Pedrosa et al.
FIG. 10. (e.1) Magnetization and (e.2) dipolar field patterns of a 0.7 eccen-
tricity, 228.6 nm long axis ellipsoidal cluster of 9 nm diameter Fe3O4 nano-
particles distributed uniformly, with a center-to-center distance of 10.98 nm.
The panels correspond to an external field strength of 0.3 kOe (point (e) in
the right inset in Fig. 5), and show the patterns at a z ¼ 0 layer of the Fe3O4
nanoparticles’ cluster. The left (right) color barcode shows the thermal aver-
age values (out-of-plane angles) of the nanoparticles’ magnetization (e.1)
and the local dipolar field (e.2).
Notice that as the external field strength decreases, the nano-
particle moments align gradually with the dipolar field. Also,
there is a gradual increase in the thermal average value of
the nanoparticle magnetic moments and the dipolar field
strength, reaching 91% of the saturation value and 0.98 kOe
in the VS at remanence, as shown in Fig. 16.
We also show in Fig. 13 the magnetization and suscepti-
bility of 390.7 nm long axis (eccentricity of 0.97) ellipsoidal
clusters of 12 nm diameter Fe3O4 nanoparticles distributed
uniformly, with a center-to-center distance of 18.93 nm. The
chosen center-to-center distance corresponds to the maxi-
mum packing density for which the cluster is superparamag-
netic. The large susceptibility (v/v0  16) corresponds to
magnetization changes in a rather narrow external field inter-
val, starting at 0.033 kOe, with a sequence of phases similar
to those shown from Figs. 6 to 9 for the 9 nm Fe3O4 nanopar-
ticle diameter high eccentricity ellipsoidal cluster. Notice
that although the relative susceptibilities of the 0.97
J. Appl. Phys. 123, 233902 (2018)
FIG. 11. (f.1) Magnetization and (f.2) dipolar field patterns of a 0.7 eccen-
tricity, 228.6 nm long axis ellipsoidal cluster of 9 nm diameter Fe3O4 nano-
particles distributed uniformly, with a center-to-center distance of 10.98 nm.
The panels correspond to an external field strength of 0.068 kOe (point (f) in
the right inset in Fig. 5), and show the patterns at a z ¼ 0 layer of the Fe3O4
nanoparticles’ cluster. The left (right) color barcode shows the thermal aver-
age values (out-of-plane angles) of the nanoparticles’ magnetization (f.1)
and the local dipolar field (f.2).
eccentricity 9 nm and 12 nm diameter Fe3O4 nanoparticle
ellipsoidal clusters are nearly the same (v/v0  16), the
12 nm cluster has a 2.5 fold larger susceptibility, since the
isolated nanoparticle susceptibility (v0) is proportional to the
nanoparticle’s volume.
Superparamagnetic nanoparticles arranged with nearly
uniform density in linear chains provide a rather special sce-
nario for the investigation of dipolar induced ferromagne-
tism. For these systems, the effect of an external field
applied along the chain direction is amplified by the nanopar-
ticle dipolar interaction, since the dipolar field is parallel to
the external field.
Self-assembly has been used to form chains of closely
packed superparamagnetic Fe and Co nanoparticles, on quasi-
one-dimensional arrays, with no preferential crystallographic
orientation.31,32 The nanoparticle arrays consisted of microme-
ter long chains, with the chain-to-chain distance larger than the
average nanoparticle spacing within the chains.
233902-9 Pedrosa et al.
FIG. 12. (g.1) Magnetization and (g.2) dipolar field patterns of a 0.7 eccen-
tricity, 228.6 nm long axis ellipsoidal cluster of 9 nm diameter Fe3O4 nano-
particles distributed uniformly, with a center-to-center distance of 10.98 nm.
The panels correspond to the patterns at remanence (point (g) in the right
inset in Fig. 5), and show the patterns at a z ¼ 0 layer of the Fe3O4 nanopar-
ticles’ cluster. The left (right) color barcode shows the thermal average val-
ues (out-of-plane angles) of the nanoparticles’ magnetization (g.1) and the
local dipolar field (g.2).
It was shown31 that the dipolar interaction may either
control the initial magnetic susceptibility, preserving the
superparamagnetic character of the Fe nanoparticles, or
stabilize the ferromagnetic order. At room temperature,
3.3 6 1.8 nm and 5.1 6 2.8 nm diameter Fe nanoparticles
chains, with an average interparticle spacing of 6.8 nm and
8.6 nm, exhibited superparamagnetic behavior with a
remarkable increase in susceptibility, by a factor larger than
10, from the 3.3 nm diameter Fe nanoparticle chains to the
5.1 nm diameter Fe nanoparticle chains. 6.7 6 3.2 nm diame-
ter Fe nanoparticle chains, with an average interparticle
spacing of 9.2 nm, exhibited ferromagnetic order with a coer-
civity of 0.22 kOe.
As shown in Table II, we have reproduced the experi-
mental data, using micrometer long chains of 4.1 nm, 6.3 nm,
and 8.9 nm diameter Fe nanoparticles, and the interparticle
spacing corresponding to the reported values. We have also
assumed that the main dipolar interaction is restricted to
J. Appl. Phys. 123, 233902 (2018)
FIG. 13. (i) Magnetization and (ii) relative susceptibility of spherical clus-
ters with 10 nm, 11 nm, and 12 nm Fe3O4 nanoparticles, distributed uni-
formly with a center-to-center distance 10% larger than the nanoparticle
diameter, and of a 390.7 nm long axis (eccentricity of 0.97) ellipsoidal clus-
ters of 12 nm diameter Fe3O4 nanoparticles distributed uniformly, with a
center-to-center distance of 18.93 nm. The magnetizations are shown in units
of the isolated nanoparticles’ saturation values and the susceptibilities are
shown in units of the isolated nanoparticles’ susceptibility.
contributions from each individual chain, since the chain-
to-chain distance is three times larger than the nanoparticle
spacing within the chains.
Similar results were reported for quasi-one-dimensional
Co nanoparticle chains,32 revealing room temperature
dipolar ferromagnetism of 5.1 nm and 5.9 nm diameter Co
nanoparticle chains, with coercivities of 0.133 kOe and
0.185 kOe. As shown in Table II, we have also reproduced
the Co chains’ experimental data, using 5.1 nm and 5.9 nm
diameter Co nanoparticle chains, and an interparticle spacing
of 1.3 nm and 2.1 nm. We notice that the coercivities of the
8.9 nm diameter Fe chains and 5.9 nm diameter Co chains
are nearly equal, the Co magnetization (1422 emu/cm3)41 is
smaller than the Fe magnetization (1714 emu/cm3), and the
233902-10 Pedrosa et al.
FIG. 14. (a.1) Magnetization and (a.2) dipolar field patterns of a 276 nm
diameter spherical cluster of 12 nm Fe3O4 nanoparticles distributed uni-
formly, with a center-to-center distance of 13.2 nm. The panels correspond
to an external field strength of 0.9 kOe (point (a) in Fig. 13) and show the
patterns at a z ¼ 0 layer of the Fe3O4 nanoparticles’ cluster. The left (right)
color barcode shows the thermal average values (out-of-plane angles) of the
nanoparticles’ magnetization (a.1) and the local dipolar field (a.2).
Fe nanoparticles are larger than the Co nanoparticles.
Therefore, in order to stabilize the dipolar ferromagnetic
phase, a smaller Co interparticle distance is required.
Experimental reports indicate that clustering of super-
paramagnetic nanoparticles in nearly spherical volumes
J. Appl. Phys. 123, 233902 (2018)
FIG. 15. (b.1) Magnetization and (b.2) dipolar field patterns of a 276 nm
diameter spherical cluster of 12 nm Fe3O4 nanoparticles distributed uni-
formly, with a center-to-center distance of 13.2 nm. The panels correspond
to an external field strength of 0.41 kOe (point (b) in Fig. 13) and show the
patterns at a z ¼ 0 layer of the Fe3O4 nanoparticles’ cluster. The left (right)
color barcode shows the thermal average values (out-of-plane angles) of the
nanoparticles’ magnetization (b.1) and the local dipolar field (b.2).
leads to reduction in the initial magnetic susceptibility and
the heat performance.33,34
Room temperature dc magnetization loops of Fe3O4
nanoparticle spherical clusters33 revealed a low field suscep-
tibility lower than the isolated nanoparticle value. The
233902-11 Pedrosa et al. J. Appl. Phys. 123, 233902 (2018)

TABLE II. Fe and Co chains.

Exp. Theory
Nanoparticle
diameter Hc(kOe) v0 Hc v0

3.3 6 1.8 nma …  1.03 … 1.07

5.1 6 2.8 nma …  11.12 … 11.2
6.7 6 3.2 nma 0.22 … 0.21 …
5.1 nmb 0.13 … 0.13 …
5.9 nmb 0.18 … 0.18 …

a
Fe chains with external field applied along the chains.31
b
Co chains with external field applied along the chains.32

packing density corresponds to a 33% average volume frac-

tion of magnetite per cluster.
As seen in Table III, we have reproduced the suscepti-
bility reduction using a 140 nm diameter spherical cluster of
densely packed 10 nm diameter Fe3O4 nanoparticles with
13 nm center-to-center interparticle distance, and a 29%
average percentage volume of magnetite per cluster.
A much larger reduction of 46.5% in the initial sus-
ceptibility, and a nearly equal reduction of the specific
absorption rate (SAR), has been reported for nearly spherical
clusters of highly interacting 23 6 3 nm Fe3O4 nanocubes.34
There is a wide distribution of cluster size and nanoparti-
cle density,34 with the clusters’ diameter ranging from 112 nm
to 234 nm, holding 20 to 30 nanocubes, and the effective nano-
cube volume ranging from 24 520 nm3 to 335 441 nm3. This
corresponds to the average interparticle center-to-center dis-
tance ranging from 29 nm to 69 nm, and an average particle
density ranging from 2.8  103 to 4.0  104 nanoparticles/lm3.
As shown in Table III, we have reproduced the experi-
mental data using 23 nm diameter Fe3O4 nanoparticles, with
an interparticle center-to-center distance of 44.6 nm, uni-
formly distributed in 112 nm diameter spherical clusters,
with a nanoparticle density of 3.3  104 nanoparticles/lm3.

FIG. 16. (c.1) Magnetization and (c.2) dipolar field patterns of a 276 nm
spherical cluster of 12 nm Fe3O4 nanoparticles distributed uniformly, with a
center-to-center distance of 13.2 nm. The panels correspond to the patterns
at remanence (point (c) in Fig. 13) and show the patterns at a z ¼ 0 layer of
the Fe3O4 nanoparticles’ cluster. The left (right) color barcode shows the
thermal average values (out-of-plane angles) of the nanoparticles’ magneti-
zation (c.1) and the local dipolar field (c.2).
IV. SUMMARY
In summary, we have discussed the impact of the dipolar
interaction in the magnetic phases of Fe3O4 superparamag-
netic nanoparticles arranged with uniform density in spherical
and ellipsoidal clusters. We have shown that the topological
layout, the nanoparticles’ packing density, the nanoparticles’
diameter, and the clusters’ eccentricity play a key role in the
clusters’ magnetic phases and initial susceptibility.
The role of dipolar interaction on the magnetic phases of
nanoparticle clusters is largely controlled by intrinsic anisot-
ropy of the dipolar field and the cluster topology. As dis-
cussed in Sec. III, using Eq. (2), the dipolar interaction favors
the parallel arrangement of nanoparticle magnetic moment
TABLE III. Fe3O4 nanoparticle spherical clusters.

v/v0
spherical clusters have a wide size distribution, with diame-
ters ranging from 70 nm to 250 nm, holding from 100 to Nanoparticle diameter Exp. Theory
10 000 nanoparticles, corresponding to an average center- (10 nm) 33
0.814 0.814
to-center nanoparticle distance ranging from 15 nm to (23 nm)34 0.536 0.533
11.6 nm. The mean diameter is 146 nm, and the magnetite
233902-12 Pedrosa et al.
pairs if they are arranged along the direction of the magnetic
moments.
We note that for spherical clusters, the direction of the
external field with respect to the cubic axis is not a key issue.
In this case, one expects the cluster to display spherical sym-
metry. In other words, as discussed in Sec. III, for any direc-
tion of the external field, the sequence of magnetic phases
from saturation to remanence will be the same, and the initial
susceptibility will be smaller than the isolated nanoparticle
initial susceptibility.
For ellipsoidal clusters, following the discussion based
on Eq. (2) in Sec. III, one may anticipate that the sequence
of magnetic phases, from saturation to remanence, and the
initial susceptibility, depends strongly on the direction of the
external field with the cubic axis.
For instance, as discussed presently, if the external field
is applied along the major axis direction, the dipolar field at
most nanoparticles is parallel to the external field. Thus, the
uniform state, with all nanoparticles magnetic moments along
the external field direction, is stable until rather small values
of the external field, leading to large susceptibility enhance-
ment. This effect is optimized for nanoparticles arranged in
linear chains because, in this case, the dipolar field acting at
the whole set of nanoparticles is parallel to the external field.
This allows the formation of nanoparticle chains in ferro-
fluids. In this case, one expects maximum susceptibility
enhancement, and the initial susceptibility is likely to be
larger than the isolated nanoparticle susceptibility.
However, if the external field is applied along the minor
axis direction, the dipolar interaction may destroy the ferro-
magnetic order, even for large values of the external field. In
this case, the central nanoparticle in the 228.6 nm long axis
ellipsoidal cluster with an eccentricity of 0.97 is surrounded
by 288 nanoparticles out of which only 14% are dipolar cou-
pled ferromagnetically to the central nanoparticle.
We have focused on purely dipolar systems, neglecting
contributions from the nanoparticles’ anisotropy energy. We
note that this limit is appropriate for large nanoparticle
packing density, with a prevalence of the inter-particle dipolar
interaction. This has been found, for instance, in key experi-
mental reports of dipolar ferromagnetism in nanoparticles sys-
tems with no preferential crystallographic orientation,27–32
indicating that regardless of the values of the anisotropy
energy, the interparticle dipolar interaction suffices to stabilize
the ferromagnetic order.
Our main goal is to investigate the magnetic properties
of clusters of superparamagnetic nanoparticles and find out
under what conditions one may optimize the cluster mag-
netic properties for biomedical applications. As such, it is
important to keep the cluster superparamagnetic, as the
nanoparticles, considered as isolated units, originally were.
In other words, the nanoparticle cluster should have no rema-
nence or coercivity, as the individual isolated nanoparticles.
The idea behind this interpretation of superparamagnet-
ism as a safe property of systems for biomedical applica-
tions, originates in the belief that one should have systems
that produce no magnetic field, unless an external field is
applied. In other words, one uses the belief that the time
J. Appl. Phys. 123, 233902 (2018)
window for biological processes is of the same order as that
for magnetization measurements.
In fact, behind the whole idea is the phenomenon of
thermal relaxation, which is commonly used explicitly in the
more restrictive scenario of the interpretation of M€osbauer
measurements, and expressed in terms of a relaxation time.
For isolated nanoparticles, with two anisotropy energy
minima, such as uniaxial anisotropy nanoparticles, one may
define a relaxation time by using the value of the energy bar-
rier to be transposed to go from one minimum to the other
minimum. This is the key outcome of the Arrhenius-Nèel
model which has been extended in special cases to interact-
ing nanoparticles,46 by calculations of the energy barriers
separating two energy minima. However, for systems com-
posed of hundreds of nanoparticles, as in our current investi-
gation, it is difficult to set up a relaxation time because there
is a rather large number of possible equilibrium states, and
thousands of ways of going from one possible minimum to
another energy minimum. Thus, there is no clear indication
on the way to follow from one energy minimum to another,
and to calculate an effective energy barrier to characterize
the relaxation time of the magnetization.
We have extended previous results25,26 and discussed the
impact of two genuinely dipolar magnetic states, the DSFS
and the VS, in the nanoparticle cluster magnetic phases.
The DSFS comprises lines along the external field direc-
tion with the orientation of the moments with the external
field resembling that of the spin flop state of two-sublattice
uniaxial antiferromagnets. The VS consists of an arrange-
ment of the nanoparticle magnetic moments resembling the
vortex state of ferromagnetic materials.
Reducing the external field strength from the saturation
value, we have found that large eccentricity ellipsoidal clus-
ters stay saturated down to small external field values, when
the DSFS is formed. Large magnetization drops start at
external fields of the order of a few Oersteds, leading to large
susceptibility values. The susceptibility may be an order of
magnitude larger than the single nanoparticle value.
For spherical clusters, the DSFS is formed at larger
external field values. The magnetization changes in an exter-
nal field interval of the order of a few hundred Oe, leading to
susceptibilities smaller than the isolated single nanoparticle
values. Regardless of the nanoparticle’s diameter, clustering
leads to a reduction of the initial susceptibility. The reduc-
tion is larger, the larger the packing density and the nanopar-
ticle size.
At remanence, the nanoparticle cluster magnetic phases
have a unique property. The dipolar energy leads to thermal
stabilization of the individual nanoparticle moments. Large
nanoparticle packing densities may allow a nearly full ther-
mal value of the nanoparticle magnetic moments. Despite
this, the nanoparticle clusters are superparamagnetic, with a
vanishingly small magnetization in the absence of an exter-
nal field, as required for biomedical safety.
We have applied the theoretical model and reproduced the
main features of previous experimental results, either reporting
susceptibility enhancement or dipolar ferromagnetism in large
nanoparticle packing density Fe and Co linear chains. We have
also reproduced experimental results reporting the reduction of
233902-13 Pedrosa et al.
the initial susceptibility of spherical clusters of Fe3O4 superpar-
amagnetic nanoparticles.
ACKNOWLEDGMENTS
The authors acknowledge support from CNPq, CAPES,
FAPERN, and the DFTE Computing Laboratory Group. The
work of A. S. Carriço and A. L. Dantas was supported by
CNPq Grant Nos. 350773 and 309676.
1
E. Peng, F. Wang, and J. M. Xue, J. Mater. Chem. B 3, 2241 (2015).
2 28
A. Kostopoulou and L. Alexandros, Nanotechnol. Rev. 4, 595 (2015).
3
E. C. Abenojar, S. Wickramasinghe, J. Bas-Concepcion, and A. C. S.
Samia, Prog. Nat. Sci.: Mater. Int. 26, 440 (2016).
4
S. Bedanta and W. Kleemann, J. Phys. D: Appl. Phys. 42, 013001 (2009).
5 30
A. K. A. Silva, E. L. Silva, J. F. Carvalho, T. R. F. Pontes, R. P. A. Neto,
A. S. Carriço, and E. S. T. Egito, Key Eng. Mater. 441, 357 (2010).
6 31
W. Wu, C. Z. Jiang, and V. A. Roy, Nanoscale 8, 19421 (2016).
7 32
E. A. Perigo, G. Hemery, O. Sandre, D. Ortega, E. Garaio, F. Plazaola,
and F. J. Teran, Appl. Phys. Rev. 2, 041302 (2015).
8
R. M. Fratila, S. Rivera-Fernandez, and J. M. de la Fuente, Nanoscale 7,
8233 (2015).
9
C. L. Dennis, A. J. Jackson, J. A. Borchers, R. Ivkov, A. R. Foreman, J.
W. Lau, E. Goernitz, and C. Gruettner, J. Appl. Phys. 103, 07A319 (2008).
10
C. L. Dennis, A. J. Jackson, J. A. Borchers, P. J. Hoopes, R. Strawbridge,
A. R. Foreman, J. van Lierop, C. Gr€ uttner, and R. Ivkov, Nanotechnology
20, 395103 (2009).
11
S. Bedanta, O. Petracic, and W. Kleemann, in Handbook of Magnetic
Materials, edited by K. J. H. Buschow (Elsevier, New York, 2015), Vol.
23.
12
S. Bedanta, T. Seki, H. Iwama, T. Shima, and K. Takanashi, Appl. Phys.
Lett. 107, 152410 (2015).
13
S. Mørup, Hyperfine Int. 90, 171 (1994).
14
S. Mørup, M. F. Hansen, and C. Frandsen, Beilstein J. Nanotechnol. 1, 182
(2010).
15
H. Marie, L. Lemaire, F. Franconi, S. Lajnef, Y. M. Frapart, V. Nicolas,
and S. Lesieur, Adv. Funct. Mater. 25, 1258 (2015).
16
G. Bealle, R. Di Corato, J. Kolosnjaj-Tabi, V. Dupuis, O. Clement, F.
Gazeau, and C. Menager, Langmuir 28, 11834 (2012).
17
J. H. Park, G. von Maltzahn, L. Zhang, M. P. Schwartz, E. Ruoslahti, S. N.
Bhatia, and M. J. Sailor, Adv. Mater. 20, 1630 (2008).
18
N. Schleich, P. Sibret, P. Danhier, B. Ucakar, S. Laurent, R. N. Muller,
and F. Danhier, Int. J. Pharm. 447, 94 (2013).
19
F. Ye, Å. Barrefelt, H. Asem, M. Abedi-Valugerdi, I. El-Serafi, M.
Saghafian, and M. Hassan, Biomaterials 35, 3885 (2014).
J. Appl. Phys. 123, 233902 (2018)
20
M. Wu, D. Zhang, Y. Zeng, L. Wu, X. Liu, and J. Liu, Nanotechnology
26, 115102 (2015).
21
C. E. Smith, J. Lee, Y. Seo, N. E. Clay, J. Park, A. Shkumatov, and B.
Andrade, ACS Appl. Mater. Interfaces 9, 1219 (2017).
22
I. Andreu, E. Natividad, L. Solozabal, and O. Roubeau, ACS Nano 9, 1408
(2015).
23
J. M. Luttinger and L. Tisza, Phys. Rev. 70, 954 (1946).
24
M. H. Cohen and F. Keffer, Phys. Rev. 99, 1128 (1955).
25
P. I. Belobrov, R. S. Gekhtch, and V. A. Ignatchenko, Sov. Phys. JETP 57,
636 (1983).
26
A. Yu. Galkin and B. A. Ivanov, JETP Lett. 83, 383 (2006).
27
K. Yamamoto, S. A. Majetich, M. R. McCartney, M. Sachan, S.
Yamamuro, and T. Hirayama, Appl. Phys. Lett. 93, 082502 (2008).
K. Yamamoto, C. R. Hogg, S. Yamamuro, T. Hirayama, and S. A.
Majetich, Appl. Phys. Lett. 98, 072509 (2011).
29
M. Var on, M. Beleggia, T. Kasama, R. J. Harrison, R. E. Dunin-
Borkowski, V. F. Puntes, and C. Frandsen, Sci. Rep. 3, 1234 (2013).
S. Yamamuro, K. Yamamoto, D. L. Peng, T. Hirayama, and K.
Sumiyama, Appl. Phys. Lett. 90, 242510 (2007).
A. Sugawara and M. R. Scheinfein, Phys. Rev. B 56, R8499 (1997).
A. Sugawara, IEEE Trans. Magn. 37, 2123 (2001).
33
D. X. Chen, A. Sanchez, H. Xu, H. Gu, and D. Shi, J. Appl. Phys. 104,
093902 (2008).
34
M. E. Materia, P. Guardia, A. Sathya, M. P. Leal, R. Marotta, R. Di
Corato, and T. Pellegrino, Langmuir 31, 808 (2015).
35
F. C. Medeiros Filho, L. L. Oliveira, S. S. Pedrosa, G. O. G. Rebouças,
and A. S. Carriço, Phys. Rev. B 92, 064422 (2015).
36
C. M. Souza, A. L. Dantas, I. S. Queiroz, Jr., and A. S. Carriço, J. Appl.
Phys. 115, 17D110 (2014).
37
A. L. Dantas, I. Queiroz, Jr., G. O. G. Rebouças, M. G. Dias, and A. S.
Carriço, J. Appl. Phys. 113, 17D710 (2013).
38
F. F. Oliveira, T. R. S. Moura, A. S. Carriço, A. L. Dantas, and G. O. G.
Rebouças, J. Appl. Phys. 111, 07D102 (2012).
39
G. O. G. Rebouças, A. S. W. T. Silva, A. L. Dantas, R. E. Camley, and A.
S. Carriço, Phys. Rev. B 79, 104402 (2009).
40
V. D. Mello, A. L. Dantas, and A. S. Carriço, Solid State Commun. 140,
447 (2006).
41
B. D. Cullity and C. D. Graham, Introduction to Magnetic Materials, 2nd
ed. (John Wiley and Sons, Inc., Hoboken, New Jersey, 2009).
42
P. Vargas, D. Altbir, and J. dAlbuquerque e Castro, Phys. Rev. B 73,
092417 (2006).
43
D. Kechrakos, K. N. Trohidou, and M. Vasilakaki, J. Magn. Magn. Mater.
316, e291 (2007).
44
G. Margaris, K. N. Trohidou, and J. Nogues, Adv. Mater. 24, 4331 (2012).
45
See http://www.ctcms.nist.gov/rdm/mumag.org.html for instance.
46
P. V. Hendriksen, G. Christiansen, and S. Mørup, J. Magn. Magn. Mater.
132, 207 (1994).