APPLIED PHYSICS LETTERS 93, 022504 共2008兲

Synthesis and magnetic properties of self-assembled FeRh nanoparticles

Z. Jia,1 J. W. Harrell,2 and R. D. K. Misra1,a兲
1
Center for Structural and Functional Materials, University of Louisiana at Lafayette, P.O. Box 44130,
Lafayette, Louisiana 70504-4130, USA
2
Center for Materials for Information Technology, University of Alabama, P.O. Box 870209, Tuscaloosa,
Alabama 35487-0209, USA
共Received 15 April 2008; accepted 9 June 2008; published online 15 July 2008兲
We report here the synthesis and magnetization behavior of tunable FeRh magnetic nanoparticles
with both controllable composition and size. FexRh1−x 共x = 0.35, 0.44, 0.51兲 nanoparticles of
4 – 20 nm size range were fabricated using a polyol coreduction process. The stoichiometry of
FexRh1−x nanoparticles was altered by tuning the molar ratio of rhodium acetylacetonate and iron
acetylacetonate. The particle size was tunable via control of surfactant concentration. Magnetic
measurements were made for films of the particles cast onto silicon wafers. The coercivity of
Fe51Rh49 nanoparticles was ⬃250 Oe at room temperature after annealing at 700 ° C for 2 h,
indicating CsCl-type phase transition. The temperature dependent magnetization measurement of
annealed Fe51Rh49 confirmed the antiferromagnetic-ferromagnetic transition and was supported by
x-ray diffraction measurements. © 2008 American Institute of Physics. 关DOI: 10.1063/1.2952956兴

The synthesis and assembly of magnetic nanoparticles
have attracted significant attention because of their potential
applications in ultrahigh-density magnetic recording.1,2 Fer-
romagnetic 共FM兲 nanoparticles can support single magnetic
domains and potentially lead to dramatic increase in storage
density. The ordered L10 phase of FePt exhibits high magne-
tocrystalline anisotropy 共Ku ⬃ 7 ⫻ 107 ergs/ cm3兲 and enables
the use of thermally stable nanoparticles of 3 – 4 nm as the
basic unit for recording. Higher recording densities can be
obtained by reducing the magnetic grain size and the width
of the grain size distribution in the recording media to keep
media noise within the acceptable limits. Further increasing
is limited by thermal instabilities when the magnetic energy
per grain KuV 共Ku is magnetocrystalline anisotropy and V is
grain volume兲 becomes comparable with thermal energies
kBT 共the superparamagnetic limit兲. FePt has high Ku values
but cannot be written by conventional recording heads. Bulk
FeRh are characterized by a first order antiferromagnetic
共AF兲 to FM transition between 50 and 100 ° C depending on
the composition.3,4 By magnetic coupling between FePt and
FeRh at AF-FM transition temperatures of FeRh, it is pos-
sible to lower the coercivity of FePt.5,6 This can be realized
by locally heating the media and lowering the coercivity dur-
ing writing,7 allowing one to overcome write field limitations
in both longitudinal and perpendicular magnetic recordings.8
Thus, there is a need to synthesize FeRh with controllable
composition and narrow size distribution.9–11 Ko et al. have
synthesized a series of FeRh nanoparticles with controllable
composition and they have systematically studied the tem-
perature dependent magnetization of nanoparticles.11 In their
studies, the average particle size was 3 – 5 nm.
This paper is focused on the synthesis and magnetic be-
havior of FeRh nanoparticles with both controllable and tun-
able size and composition. The synthesis yielded average
particles sizes from 4 to 20 nm.
Monodisperse FeRh nanoparticles were synthesized us-
ing a chemical coreduction process involving reduction of
a兲
Author to whom correspondence should be addressed. Electronic mail:
dmisra@louisiana.edu.
iron 共III兲 acetylacetonate 关Fe共acac兲3兴 and rhodium 共III兲
acetylacetonate 关Rh共acac兲3兴 using 1,12-dodecanediol in the
presence of oleic acid, oleylamine, and phenyl ether 共25 ml兲.
The synthesis was carried out in nitrogen atmosphere and the
temperature of the mixed constituents was increased to
100 ° C for 10 min to ensure that the precursors dissolved.
Subsequently, the temperature was raised to 200 ° C and
maintained for 2 h. This was followed by increasing the tem-
perature of the solution to reflux at 260 ° C for 1 h After the
synthesis, the product solution was cooled to room tempera-
ture. The precipitation and purification processes were re-
peatedly carried out a minimum of three to four times, and
the final product was finally dispersed in hexane. Structural
characterization of particles was carried out using transmis-
sion electron microscopy 共TEM兲 and x-ray diffraction
共XRD兲. The magnetic properties were measured by the su-
perconducting quantum interference device 共SQUID兲 magne-
tometer for nanoparticle film annealed in oven at 700 ° C for
2 h.
A series of FeRh nanoparticles with different composi-
tions was synthesized by changing the ratio of the precursors
关Fe共acac兲3 : Rh共acac兲3 ratio兴. The 1.2 ratio of
Fe共acac兲3 : Rh共acac兲3 yielded FeRh nanoparticle stoichiom-
etry composition of Fe35Rh65 with size of 20 nm. The 1.8
ratio of Fe共acac兲3 : Rh共acac兲3 was required to obtain FeRh
with composition of Fe51Rh49 with size of 20 nm. The inter-
mediate 1.6 ratio of Fe共acac兲3 : Rh共acac兲3 gives FeRh nano-
particles with composition of Fe44Rh56 of 20 nm.
Given that the aim is to fabricate FeRh 共Fe50Rh50兲 nano-
particles, the experimentally synthesized Fe51Rh49 was se-
lected for further studies. TEM images of as-synthesized
Fe51Rh49 nanoparticles with different concentrations of sur-
factant oleic acid and oleylamine used in the synthesis pro-
cess are presented in Fig. 2. The size distribution in the 20
and 10 nm FeRh nanoparticle images is narrow while the
4 nm one shows bimodal distribution. The molar ratio of
Fe共acac兲3 and Rh共acac兲3 was maintained constant at 1.8 and
the content of oleic acid and oleylamine was varied to obtain
different nanoparticle sizes-as described in Fig. 1. 1 ml of

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022504-2 Jia, Harrell, and Misra Appl. Phys. Lett. 93, 022504 共2008兲

FIG. 1. TEMs of Fe51Rh49 nanoparticles with different amounts of surfac-

tant 共a兲 1 ml 共average size: 20 nm兲, 共b兲 0.5 ml 共average size: 10 nm兲, and 共c兲
0.25 ml 共average size: 4 nm兲 of oleic acid and oleylamine.

oleic acid and 1 ml of oleyamine gave an average Fe51Rh49

nanoparticle size of 20 nm, 0.5 ml of oleic acid and 0.5 ml
of oleyamine yielded an average Fe51Rh49 nanoparticle size
of 10 nm, and 0.25 ml of oleic acid and 0.25 ml of ole-
yamine gave an average Fe51Rh49 nanoparticle size of 4 nm.
XRD analysis of Fe51Rh49 nanoparticles is presented in
Fig. 2. The XRD pattern of as-synthesized 4 nm Fe51Rh49
nanoparticles shows the 共100兲 and 共111兲 peaks of chemical-
disordered ␥-FeRh phase 共fcc兲. On annealing at 700 ° C for
2 h, the 共110兲 peak of the chemically ordered FeRh in the
XRD pattern indicated partial transformation of ␥-FeRh
phase to the ␣⬘-FeRh phase 共bcc兲, which is AF. The 共110兲
peak indicates the CsCl-type structure 共␣⬘-FeRh兲 formation,
while the presence of 共100兲 and 共111兲 peaks of ␥-FeRh sug-
gests that FeRh is not completely transformed into ␣⬘-FeRh.
The appearance of the Rh 共111兲 peak and the Fe 共110兲 peak
presumably implies the partial precipitation of the parent el-
ements from the FeRh alloy.
The hysteresis loop for as-synthesized and annealed
共700 ° C for 2 h兲 Fe51Rh49 nanoparticles measured at room
temperature 共300 K兲 is presented in Fig. 3. The coercivity
共Hc兲 of as-deposited FeRh nanoparticles was very small and
nearly zero, while the coercivity of annealed Fe51Rh49 nano-
particles was ⬃250 Oe. This increase is most likely because
of the increase of particle size on annealing.
FIG. 3. Hysteresis loops of 共a兲 as-synthesized and 共b兲 annealed 20 nm
Fe51Rh49 nanoparticles.
Figure 4 presents the magnetization as a function of tem-
perature for Fe51Rh49 nanoparticles at an applied field of
10 kOe for as-synthesized and annealed 共700 ° C for 2 h兲
samples. In the case of as-synthesized Fe51Rh49 nanopar-
ticles, during the heating process, the magnetization de-
creased from 270 K and reached the minimum at 370 K fol-
lowed by an increase up to 400 K. While on cooling from
400 to 270 K, the magnetization continuously increased dur-
ing the cooling process. The likely reason for this tempera-
ture dependence is that the as-synthesized FeRh particles are
superparamagnetic and there is a small amount of AF
␣⬘-FeRh formed due to the compositional inhomogeneity
from particle to particle in that temperature range. Further-
more, the high temperature of reflux during the synthesis

FIG. 4. Dependence of magnetization on temperature of Fe51Rh49 nanopar-

FIG. 2. XRD patterns of 共a兲 as-prepared, and 共b兲 700 ° C, 2 h annealed 4 nm ticles: 共a兲 as-prepared and 共b兲 annealed at 700 ° C for 2 h at an applied field
Fe51Rh49 nanoparticles. of 10 kOe.
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022504-3 Jia, Harrell, and Misra
共260 ° C兲 could cause partial ordering of the synthesized par-
ticles. The decrease in magnetization during the heating pro-
cess until 370 K is typical for superparamagnetic materials.
Subsequently, the AF ␣⬘-FeRh might transform into FM
␣⬘-FeRh 共bcc兲. This FM ␣⬘-FeRh contributed to the increase
of the magnetization between 370 and 400 K. It is noted that
this phase transition is not reversible in the cooling process
over the temperature range of the measurements. On cooling,
the magnetization of superparamagnetic ␥-FeRh and FM
␣⬘-FeRh increases continuously from 400 to 270 K in a
manner similar to superparamagnetic material and ferromag-
nets. The higher total magnetization during the cooling pro-
cess than during the heating process is attributed to the re-
tention of the ␣⬘-FeRh. It is not fully understood why the
FM ␣⬘-FeRh does not transform back into AF ␣⬘-FeRh. This
may be related to the small amount of ordering produced
during the synthesis and the fact that the maximum tempera-
ture during the magnetization measurements 共400 K兲 was
not enough to produce additional ordering.
In contrast, the annealed Fe51Rh49 nanoparticles exhib-
ited a distinct AF to FM transition during both the heating
and cooling processes. There is a temperature hysteresis ob-
served on the magnetization versus temperature plot in a
constant in-plane field of 10 kOe. This is consistent with the
FeRh/ MgO thin film system.5 The temperature range at each
magnetization during heating and cooling processes remains
the same for the FeRh thin film.5 However, the temperature
range is larger at lower magnetization and smaller at higher
magnetization for FeRh nanoparticles. Furthermore, the
phase transition occurred over a wide range of temperature
compared to that of thin film FeRh samples.5 The widening
of the temperature hysteresis is similar to polycrystalline
FeRh thin film on SiN,12 and is presumably due to the dis-
tribution in ordering or particle size. It is noted that the mag-
netization of annealed FeRh is not zero below the transition
temperature, implying that two phases 共FM and AF phases兲
exist in the annealed FeRh at room temperature. The coex-
istence of FM ␣⬘-FeRh and AF ␣⬘-FeRh is possibly due to
Downloaded 16 Jul 2008 to 130.70.139.46. Redistribution subject to AIP license or copyright; see http://apl.aip.org/apl/copyright.jsp
Appl. Phys. Lett. 93, 022504 共2008兲
the inhomogeneous composition in the nanoparticles, array.
It is likely that the maximum measuring temperature of
400 K was not adequate to completely obtain the FM phase.
The XRD pattern shows the 共110兲 peak of iron in the an-
nealed FeRh. The magnetization below transition tempera-
ture is relatively large. If we were able to go to much higher
temperatures in the SQUID, then the low temperature mag-
netization would be relatively small.
In summary, we have synthesized FeRh nanoparticles
with both controllable composition and size. The use of high
volume surfactants 共oleic acid and oleylamine兲 in the precur-
sor increases the size of nanoparticles at constant iron acety-
lacetonate and rhodium acetylacetonate ratio. Temperature
dependent magnetization and XRD measurements suggest
the transformation of the AF phase to the FM phase. How-
ever, the transformation occurs over a wide temperature
range compared to that of thin film FeRh samples.
The authors gratefully acknowledge financial support
from Information Technology Initiative program of Louisi-
ana Board of Regents for the work presented here.
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