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Synthesis and magnetic properties of self-assembled FeRh nanoparticles

Z. Jia,1 J. W. Harrell,2 and R. D. K. Misra1,a兲
Center for Structural and Functional Materials, University of Louisiana at Lafayette, P.O. Box 44130,
Lafayette, Louisiana 70504-4130, USA
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 iron 共III兲 acetylacetonate 关Fe共acac兲3兴 and rhodium 共III兲
have attracted significant attention because of their potential acetylacetonate 关Rh共acac兲3兴 using 1,12-dodecanediol in the
applications in ultrahigh-density magnetic recording.1,2 Fer- presence of oleic acid, oleylamine, and phenyl ether 共25 ml兲.
romagnetic 共FM兲 nanoparticles can support single magnetic The synthesis was carried out in nitrogen atmosphere and the
domains and potentially lead to dramatic increase in storage temperature of the mixed constituents was increased to
density. The ordered L10 phase of FePt exhibits high magne- 100 ° C for 10 min to ensure that the precursors dissolved.
tocrystalline anisotropy 共Ku ⬃ 7 ⫻ 107 ergs/ cm3兲 and enables Subsequently, the temperature was raised to 200 ° C and
the use of thermally stable nanoparticles of 3 – 4 nm as the maintained for 2 h. This was followed by increasing the tem-
basic unit for recording. Higher recording densities can be perature of the solution to reflux at 260 ° C for 1 h After the
obtained by reducing the magnetic grain size and the width synthesis, the product solution was cooled to room tempera-
of the grain size distribution in the recording media to keep ture. The precipitation and purification processes were re-
media noise within the acceptable limits. Further increasing peatedly carried out a minimum of three to four times, and
is limited by thermal instabilities when the magnetic energy the final product was finally dispersed in hexane. Structural
per grain KuV 共Ku is magnetocrystalline anisotropy and V is characterization of particles was carried out using transmis-
grain volume兲 becomes comparable with thermal energies sion electron microscopy 共TEM兲 and x-ray diffraction
kBT 共the superparamagnetic limit兲. FePt has high Ku values 共XRD兲. The magnetic properties were measured by the su-
but cannot be written by conventional recording heads. Bulk perconducting quantum interference device 共SQUID兲 magne-
FeRh are characterized by a first order antiferromagnetic tometer for nanoparticle film annealed in oven at 700 ° C for
共AF兲 to FM transition between 50 and 100 ° C depending on 2 h.
the composition.3,4 By magnetic coupling between FePt and
A series of FeRh nanoparticles with different composi-
FeRh at AF-FM transition temperatures of FeRh, it is pos-
tions was synthesized by changing the ratio of the precursors
sible to lower the coercivity of FePt.5,6 This can be realized
关Fe共acac兲3 : Rh共acac兲3 ratio兴. The 1.2 ratio of
by locally heating the media and lowering the coercivity dur-
ing writing,7 allowing one to overcome write field limitations Fe共acac兲3 : Rh共acac兲3 yielded FeRh nanoparticle stoichiom-
in both longitudinal and perpendicular magnetic recordings.8 etry composition of Fe35Rh65 with size of 20 nm. The 1.8
Thus, there is a need to synthesize FeRh with controllable ratio of Fe共acac兲3 : Rh共acac兲3 was required to obtain FeRh
composition and narrow size distribution.9–11 Ko et al. have with composition of Fe51Rh49 with size of 20 nm. The inter-
synthesized a series of FeRh nanoparticles with controllable mediate 1.6 ratio of Fe共acac兲3 : Rh共acac兲3 gives FeRh nano-
composition and they have systematically studied the tem- particles with composition of Fe44Rh56 of 20 nm.
perature dependent magnetization of nanoparticles.11 In their Given that the aim is to fabricate FeRh 共Fe50Rh50兲 nano-
studies, the average particle size was 3 – 5 nm. particles, the experimentally synthesized Fe51Rh49 was se-
This paper is focused on the synthesis and magnetic be- lected for further studies. TEM images of as-synthesized
havior of FeRh nanoparticles with both controllable and tun- Fe51Rh49 nanoparticles with different concentrations of sur-
able size and composition. The synthesis yielded average factant oleic acid and oleylamine used in the synthesis pro-
particles sizes from 4 to 20 nm. cess are presented in Fig. 2. The size distribution in the 20
Monodisperse FeRh nanoparticles were synthesized us- and 10 nm FeRh nanoparticle images is narrow while the
ing a chemical coreduction process involving reduction of 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
Author to whom correspondence should be addressed. Electronic mail: the content of oleic acid and oleylamine was varied to obtain different nanoparticle sizes-as described in Fig. 1. 1 ml of

0003-6951/2008/93共2兲/022504/3/$23.00 93, 022504-1 © 2008 American Institute of Physics

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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. 3. Hysteresis loops of 共a兲 as-synthesized and 共b兲 annealed 20 nm
Fig. 2. The XRD pattern of as-synthesized 4 nm Fe51Rh49 Fe51Rh49 nanoparticles.
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 Figure 4 presents the magnetization as a function of tem-
2 h, the 共110兲 peak of the chemically ordered FeRh in the perature for Fe51Rh49 nanoparticles at an applied field of
XRD pattern indicated partial transformation of ␥-FeRh 10 kOe for as-synthesized and annealed 共700 ° C for 2 h兲
phase to the ␣⬘-FeRh phase 共bcc兲, which is AF. The 共110兲 samples. In the case of as-synthesized Fe51Rh49 nanopar-
peak indicates the CsCl-type structure 共␣⬘-FeRh兲 formation, ticles, during the heating process, the magnetization de-
while the presence of 共100兲 and 共111兲 peaks of ␥-FeRh sug- creased from 270 K and reached the minimum at 370 K fol-
gests that FeRh is not completely transformed into ␣⬘-FeRh. lowed by an increase up to 400 K. While on cooling from
The appearance of the Rh 共111兲 peak and the Fe 共110兲 peak 400 to 270 K, the magnetization continuously increased dur-
presumably implies the partial precipitation of the parent el- ing the cooling process. The likely reason for this tempera-
ements from the FeRh alloy. ture dependence is that the as-synthesized FeRh particles are
The hysteresis loop for as-synthesized and annealed superparamagnetic and there is a small amount of AF
共700 ° C for 2 h兲 Fe51Rh49 nanoparticles measured at room ␣⬘-FeRh formed due to the compositional inhomogeneity
temperature 共300 K兲 is presented in Fig. 3. The coercivity from particle to particle in that temperature range. Further-
共Hc兲 of as-deposited FeRh nanoparticles was very small and more, the high temperature of reflux during the synthesis
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. 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 Appl. Phys. Lett. 93, 022504 共2008兲

共260 ° C兲 could cause partial ordering of the synthesized par- the inhomogeneous composition in the nanoparticles, array.
ticles. The decrease in magnetization during the heating pro- It is likely that the maximum measuring temperature of
cess until 370 K is typical for superparamagnetic materials. 400 K was not adequate to completely obtain the FM phase.
Subsequently, the AF ␣⬘-FeRh might transform into FM The XRD pattern shows the 共110兲 peak of iron in the an-
␣⬘-FeRh 共bcc兲. This FM ␣⬘-FeRh contributed to the increase nealed FeRh. The magnetization below transition tempera-
of the magnetization between 370 and 400 K. It is noted that ture is relatively large. If we were able to go to much higher
this phase transition is not reversible in the cooling process temperatures in the SQUID, then the low temperature mag-
over the temperature range of the measurements. On cooling, netization would be relatively small.
the magnetization of superparamagnetic ␥-FeRh and FM In summary, we have synthesized FeRh nanoparticles
␣⬘-FeRh increases continuously from 400 to 270 K in a with both controllable composition and size. The use of high
manner similar to superparamagnetic material and ferromag- volume surfactants 共oleic acid and oleylamine兲 in the precur-
nets. The higher total magnetization during the cooling pro- sor increases the size of nanoparticles at constant iron acety-
cess than during the heating process is attributed to the re-
lacetonate and rhodium acetylacetonate ratio. Temperature
tention of the ␣⬘-FeRh. It is not fully understood why the
dependent magnetization and XRD measurements suggest
FM ␣⬘-FeRh does not transform back into AF ␣⬘-FeRh. This
the transformation of the AF phase to the FM phase. How-
may be related to the small amount of ordering produced
during the synthesis and the fact that the maximum tempera- ever, the transformation occurs over a wide temperature
ture during the magnetization measurements 共400 K兲 was range compared to that of thin film FeRh samples.
not enough to produce additional ordering. The authors gratefully acknowledge financial support
In contrast, the annealed Fe51Rh49 nanoparticles exhib- from Information Technology Initiative program of Louisi-
ited a distinct AF to FM transition during both the heating ana Board of Regents for the work presented here.
and cooling processes. There is a temperature hysteresis ob-
served on the magnetization versus temperature plot in a 1
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