JOURNAL OF APPLIED PHYSICS VOLUME 95, NUMBER 3 1 FEBRUARY 2004

Magnetics of ultrathin FePt nanoparticle films

G. A. Held,a) Hao Zeng, and Shouheng Sun
IBM TJ Watson Research Center, PO Box 218, Yorktown Heights, New York 10598
共Received 3 September 2003; accepted 27 October 2003兲
We present magnetization data for polymer-mediated, self-assembled films of 4 nm FePt
nanoparticles with thicknesses between one and four nanoparticle layers. As synthesized and
deposited, the assemblies contain weakly magnetic material whose volume is equivalent to an outer
0.5 nm shell of the nanoparticles. During a 580 °C anneal, this material is incorporated into the
magnetic domains of the nanoparticles. The fraction of nanoparticles transformed by annealing into
ferromagnetic L1 0 FePt, the structure essential for magnetic storage applications, is found to vary
with sample thickness; samples thinner than four nanoparticle layers show no significant fraction of
ferromagnetic 共at 300 K兲 L1 0 structured nanoparticles under these annealing conditions, while in
films comprised of four nanoparticle layers, less than half of the particles are ferromagnetic at 300
K. Possible causes of these observed results are discussed. © 2004 American Institute of Physics.
关DOI: 10.1063/1.1635669兴

I. INTRODUCTION have carried out detailed magnetization measurements on as-

For the areal density of magnetic recording media to
continue increasing at its current rate, it will be necessary to
develop magnetic materials which can support increasingly
smaller bits.1 Media comprised of highly anisotropic FePt
nanoparticles represent one potential candidate for ultra-high
density magnetic storage.2 The synthesis of FePt nanopar-
ticles, which exhibit magnetic hysteresis at room tempera-
ture, has been reported,2,3 as has the self-assembly of these
particles into 120 nm films onto which 共following an anneal兲
magnetic data could be written and read back at moderate
linear densities 共5000 flux changes/mm兲. In principle, it
should be possible to store data on assemblies of exchange-
decoupled FePt nanoparticles at significantly higher densi-
ties, provided that the easy axes of the nanopaticles can be
ordered4 and assemblies can be made which are only a few
nanoparticle layers thick.1 With this goal in mind, a tech-
nique whereby a monolayer of nanoparticles is bound to a
thin polymer film has been developed.5 This technique en-
ables the depositon of FePt nanoparticles, one monolayer at a
time, over large areas. The FePt nanoparticles, as synthesized
and deposited, have a chemically disordered face centered
cubic 共fcc兲 crystalline structure and are superparamagnetic6
at 300 K 共and, thus, show no magnetic coercivity兲. Only after
being annealed do they exhibit an ordered, face-centered te-
tragonal 共fct兲 L1 0 crystal structure, a phase that is magneti-
cally hard at room temperature and viable as storage media.
However, magnetic studies of annealed assemblies have re-
vealed a decrease in coercivity with decreasing film
thickness.7 This has significant implications for the viability
of these materials as magnetic media—the presence of non-
ferromagnetic nanoparticles in such an assembly would di-
rectly reduce the maximum attainable bit density.
To address the issue of thickness dependence of the mag-
netic properties of ultra-thin nanoparticle assemblies, we
a兲
Electronic mail: gaheld@us.ibm.com
semblies of one, two, three, and four monolayers of FePt
particles, both before and after annealing at 580 °C. This
temperature was chosen because annealing at higher tem-
peratures is known to result in significant nanoparticle aggre-
gation, while annealing at lower temperatures results in re-
duced atomic ordering and magnetic coercivity.2,7 Prior to
annealing, we find that the FePt/polymer assemblies contain
particles which are superparamagnetic at room temperature,
as well as a significant amount of material which is not mag-
netically saturated at applied fields of 70 kOe. This lack of
saturation could result from a weakly magnetic outer shell,
said weakness being the result of spin canting8 as well as
interactions with surface ligands. Following a 30 min anneal,
the lack of saturation largely disappears and the principle
magnetic constituents of the assembly are superparamagnetic
nanoparticles. Further, we find that the fraction of nanopar-
ticles which exhibit hysteresis at 300 K does indeed vary
with sample thickness. For one, two, and three nanoparticle
layer samples, this fraction is zero, while for four layer
samples it is less than one-half.
II. EXPERIMENT
We synthesized 4 nm diameter Fe58Pt42 particles by wet
chemical processing, using platinum acetylacetonate and iron
chloride as precursors and following published protocols.7
Following this synthesis, the Fe58Pt42 particles were depos-
ited onto a substrate using established methods:5,7 A naturally
oxidized and double-side-polished Si substrate was im-
mersed in a chloroform solution of polyethylenimine 共PEI,
⬃20 mg/ml兲 for about 30 s, withdrawn from the solution and
dipped into ethanol to wash off the excess PEI, and dried.
The PEI functionalized substrate was immersed into the hex-
ane dispersion of FePt nanoparticles 共⬃10 mg/ml兲 for 30 s,
withdrawn from the dispersion, rinsed with hexane, and
dried. This yielded a monolayer of an FePt nanoparticle/PEI

0021-8979/2004/95(3)/1481/4/$22.00 1481 © 2004 American Institute of Physics

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1482 J. Appl. Phys., Vol. 95, No. 3, 1 February 2004
FIG. 1. 共a兲 Magnetic moment/area vs applied field for unannealed, polymer-
mediated three layer thick FePt nanoparticle assembly at 10 K. Solid line is
diamagnetic contribution of Si substrate; dashed line is best fit to slope of
the data for 兩 H applied兩 ⬎20 kOe. 共b兲 Magnetization signal 共a兲 with contribu-
tion from Si substrate 共solid line兲 subtracted. 共c兲 Magnetization signal 共a兲
with linear fit to high field data 共dotted line兲 subtracted. Solid line is best fit
of data to Langevin function 共see text兲. 共d兲, 共e兲, 共f兲 are equivalent to 共a兲, 共b兲,
共c兲 but with data taken at 300 K. Data taken at increasing magnetic fields
shown as open squares and data taken at decreasing fields shown as solid
squares.
assembly. By repeating the procedure, multilayer assemblies
of FePt nanoparticles with thicknesses of two, three, and four
nanoparticle layers were readily prepared.
Magnetization measurements were taken with a Quan-
tum Design MPMS Squid magnetometer in reciprocating
sample measurement mode. The sample substrates were
lodged into the center of a straw, with the plane of the
sample parallel to the direction of the applied field. Figures
1共a兲 and 1共d兲 show magnetization data taken at 10 and 300
K, respectively, from a three nanoparticle thick unannealed
FePt/polymer assembly. At most values of the applied field,
the signal appears dominated by the diamagnetic response of
the Si substrate. The solid lines shown in the figures corre-
spond to the diamagnetic signal, as determined by measuring
plain Si substrates, whereas the dotted lines are best fits to
the slopes of these data in their regions of linear response,
兩 H applied兩 ⬎20 kOe. Figures 1共b兲 and 1共e兲 show the data of
Figs. 1共a兲 and 1共d兲 following subtraction of the measured
diamagnetic signal, while Figs. 1共c兲 and 1共f兲 show the same
data, but with the linear fits to the high field data 关i.e., the
dotted lines in Figs. 1共a兲 and 1共d兲兴 subtracted. It follows that
the data in Figs. 1共b兲 and 1共e兲 show the full magnetization of
the FePt/polymer assembly, whereas the data in Figs. 1共c兲
and 1共f兲 show the magnetization only of those components
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Held, Zeng, and Sun
which are magnetically saturated above ⬃20 kOe.
RESULTS AND DISCUSSION
It is clear from Figs. 1共b兲 and 1共e兲 that the magnetization
of the sample has not begun to saturate at even the highest
applied fields 共70 kOe兲. This indicates that some spins are
not aligned with the nanoparticle cores—possibly due to sur-
face canting8 or interactions between metal ions and the sur-
face ligands 共for example, the formation of a surface oxide
layer兲. We fit the nonhysteretic regions of the data in Fig.
1共c兲 to the Langevin paramagnetic function, which is known
to describe the magnetization of superparamagnetic
particles:6 M (x)⫽N ␮ 关 coth x⫺(1/x) 兴 , where x⫽ ␮ H/k B T, N
is the number of nanoparticles, ␮ is the magnetic moment of
an individual nanoparticle, H is the applied field, k B is Bolt-
zmann’s constant, and T is the absolute temperature. From
the best fit value for ␮ (1.1⫻10⫺18 emu), we can obtain an
approximate value for the average size of those magnetic
domains already saturated at 20 kOe 共presumably the nano-
particle cores兲 at 10 K. Assuming a saturation magnetization
of 1030 G 关the observed value for disordered FePt 共Ref. 9兲兴,
the fit to Fig. 1共c兲 yields an average domain size of 1.3 nm.
This value is probably an underestimate; the Langevin func-
tion does not include the effects of magnetoanisotropy,
clearly present, as demonstrated by the observed hysteresis.
Note that an assembly of particles, each with a magnetic
moment of 1.1⫻10⫺18 emu, will reach 90% of saturation at
an applied field of 12 kOe at 10 K, whereas at 300 K a field
of 350 kOe would be required. This 30-fold difference in the
required applied field readily accounts for the largely unsat-
urated magnetic response observed at 300 K 关Fig. 1共e兲兴.
Plots of magnetization as a function of applied field fol-
lowing an anneal at 580 °C for 30 min under N 2 are shown in
Fig. 2; data taken at 10 K for assemblies comprised of one,
two, three, and four nanoparticle layers are shown as Figs.
2共a兲, 2共b兲, 2共c兲, and 2共d兲, respectively, while equivalent mea-
surements taken at 300 K are shown as Figs. 2共e兲, 2共f兲, 2共g兲,
and 2共h兲. These measurements show that, postanneal, the
magnetizations of all of the samples are largely saturated by
70 kOe, suggesting that most of the spins have now been
incorporated magnetically into the nanoparticles. This con-
clusion is further supported by fitting the 300 K data from
the annealed three layer sample 关Fig. 2共g兲兴 to a Langevin
paramagnetic function. Again assuming a saturation magne-
tization of 1030 G, the best fit value for the diameter of the
average superparamagnetic particle is 4 nm. This value com-
pares well with the diameter of 4 nm observed by transmis-
sion electron microscopy 共not shown兲, indicating that, post-
anneal, each nanoparticle is comprised of a single magnetic
domain.
Comparing the saturation moments observed in Figs.
1共c兲 and 2共c兲, one can estimate the volume of the magnetic
material incorporated into the single domain nanoparticles
through annealing. The saturated magnetic moment/cm2 ob-
tained from the Langevin fit to Fig. 1共c兲 is 44 ␮emu/cm2.
The equivalent fit to Fig. 2共c兲 yields 103 ␮emu/cm2. Assum-
ing the postanneal magnetic domain size to be 4 nm, the
volume of the material incorporated into these domains as a
J. Appl. Phys., Vol. 95, No. 3, 1 February 2004 Held, Zeng, and Sun 1483

FIG. 2. Magnetic moment/area vs applied field measured at 10 K for polymer-mediated FePt nanoparticle assemblies annealed at 580 °C under N 2 for 30 min
共a兲 one, 共b兲 two, 共c兲 three, and 共d兲 four nanoparticle layers thick. 共e兲, 共f兲, 共g兲, and 共h兲 show equivalent data taken at 300 K. The diamagnetization of the Si
substrate has been subtracted from all the data. The solid line in 共g兲 is a best fit to the Langevin function. The solid line in 共h兲 is a superposition of a Langevin
paramagnetic function and the hysteretic lineshape predicted for a collection of randomly oriented Stoner–Wohlfarth particles. Data taken at increasing
magnetic fields shown as open squares and data taken at decreasing fields shown as solid squares.

result of the anneal is equivalent to the outermost 0.5 nm of
these particles. Put differently, our data is consistent with,
but does not prove, a model whereby the nanoparticles as
synthesized have a 0.5 nm outer shell of weakly ferromag-
netic 共e.g., canted or ligand bound兲 material which, during
the annealing process, is incorporated into domains com-
prised of entire nanoparticles.
The data in Fig. 2 show that the saturation moment per
unit area of the nanoparticle assemblies increases monotoni-
cally 共and more or less linearly兲 with number of deposited
layers, both at 10 and 300 K. This indicates that all of the
layers are comprised of ferro- and super-paramagentic nano-
particles. The samples comprised of one, two, and three
nanoparticle layers all exhibit the behavior expected for
blocked superparamagnetic particles at 10 K, but show little
hysteresis at 300 K. This is consistent with particles com-
prised of disordered fcc FePt. It is not consistent, however,
with well-ordered 4 nm L1 0 FePt nanoparticles, as these
would exhibit hysteresis at 300 K.10 The observed corecivity
increases abruptly between the three and four layer thick
assemblies 关Figs. 2共c兲 and 2共d兲兴. This indicates that the four
layer assembly contains at least some particles with signifi-
cantly greater magnetoanisotropy than the thinner samples—
presumably L1 0 FePt. However, the observation that the co-
ercivity in Fig. 2共d兲 is only 7.6 kOe suggests that the L1 0
phase is only partially ordered.10 Further, the observation of
hysteresis in the 300 K data of Fig. 2共h兲 supports the pres-
ence of some L1 0 FePt particles in the four layer film. Note,
however, in Fig. 2共h兲, that the width of the hysteresis curve
observed at finite magnetic moments is greater than the co-
ercivity at zero moment. This unusual behavior is consistent
with an assembly comprised of both ferro- and super-
paramagnetic particles. The solid line in Fig. 2共h兲 is a best fit
of the data to a superposition of the Langevin function for 4
nm fcc FePt nanoparticles and a curve which describes the
hysteretic behavior of a collection of randomly oriented
Stoner–Wohlfarth particles.11 The coercivity of the Stoner–
Wohlfarth curve and the values of the saturation moments of
the two superimposed curves are the only adjustable param-
eters in the fit; the resulting contributions of the superpara-
magnetic and ferromagnetic curves to the solid line are 60
and 40%, respectively. The agreement between the data and
the solid line in Fig. 2共h兲 demonstrates that the observed
shape of the magnetization data at 300 K can be readily
modeled by assuming contributions to the magnetization
from both blocked and unblocked superparamagnetic par-
ticles, with a contribution of 40% from the ferromagnetic
L1 0 FePt nanoparticles in this assembly. Note that the data at
10 K 关Fig. 2共d兲兴 do not have the two phase lineshape of the
300 K data. This is consistent with a distribution in the sizes
of the magnetic domains—at very low temperatures the co-
ercivity is largely independent of particle size whereas, at
higher temperatures, large particles 共or aggregates兲 will re-
main ferromagnetic, while smaller ones 共with the same mag-
netoanisotropy兲 become superparamagnetic.1,10
In this work we have observed a clear dependence of the
magnetic behavior of annealed assemblies of FePt nanopar-
ticles on sample thickness—a result with potentially signifi-
cant technological consequences. While it is possible that
this thickness dependence could result either from the upper
layers of nanoparticles becoming oxidized or the lower lay-
ers forming a silicide structure, neither of these possibilities
are consistent with x-ray diffraction measurements,12 which
show no evidence for either iron oxides or silicides following
an anneal at 580 °C. Another possibility is that the degree of
interparticle aggregation increases with sample thickness. A
recent report indicates that larger FePt particles are more
likely to order during an anneal.13 Thus, if the four layer
sample has a greater fraction of aggregated particles, it could
be these aggregated clusters which order at 580 °C and sub-
sequently contribute a ferromagnetic component to the mag-
netization. In this case, it may be necessary to anneal above
580 °C to sufficiently order all of the nanoparticles. The
choice of ligands stabilizing the particles would then also
have to be modified, so as to prevent aggregation.14 Then,
with this encapsulation of the particles in an appropriate ma-

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1484 J. Appl. Phys., Vol. 95, No. 3, 1 February 2004 Held, Zeng, and Sun

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