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Exchange-coupled FePt nanoparticle assembly

Hao Zenga) and Shouheng Sun
IBM T. J. Watson Research Center, Yorktown Heights, New York 10598
T. S. Vedantam and J. P. Liu
Institute for Micromanufacturing, Louisiana Tech University, Ruston, Louisiana 71272
Z.-R. Dai and Z.-L. Wang
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332
共Received 21 November 2001; accepted for publication 7 February 2002兲
We have produced exchange-coupled FePt nanoparticle assemblies by chemical synthesis and
subsequent thermal annealing. As the interparticle distances decrease by tuning the annealing
conditions, interparticle interactions change from dipolar type to exchange type, and the
magnetization reversal mechanism switches from rotation controlled to domain-nucleation
controlled. With increasing annealing temperature, the coercivity first increases due to improved
chemical ordering, and then drops significantly, resulting from excessive interparticle exchange
coupling. For the samples exhibiting exchange coupling, both the remanence ratio and coercive
squareness increase. © 2002 American Institute of Physics. 关DOI: 10.1063/1.1467976兴

High-performance permanent magnets for energy-related electron microscopy and x-ray diffractometry 共XRD兲, and
applications require a large energy product (BH) max . A per- the magnetic properties were measured by a superconducting
manent magnet with a large (BH) max value should exhibit quantum interference device magnetometer. As-synthesized
both high remanent magnetization M r and large coercivity particles possess a disordered fcc structure, which are super-
H c . Both parameters are determined not only by intrinsic paramagnetic at room temperature due to small sizes and low
properties such as the magnetocrystalline anisotropy K u and anisotropy. Thermal annealing results in a phase transforma-
saturation magnetization M s , but also by structural param- tion from the disordered fcc to ordered fct structure above
eters such as grain sizes and alignment of the granular ma- 500 °C.6 All samples were annealed at temperatures between
terials. Tremendous effort has been devoted in the last cen- 500 and 800 °C for 1 h, in a flow of gas mixture of Ar
tury to improving magnetic properties of permanent ⫹H2 共5%兲. No preferential orientation of the particles is ob-
magnets,1 however, it is recently realized that nanostructured served from either XRD or electron diffractions. Previous
magnetic materials have the potential for a very high energy works have indicated that for FePt with various compositions
product.2,3 Fe54-58Pt46-42 shows the largest coercivities after annealing.7
L1 0 -ordered FePt alloys have high M s 共⬃1100 Here, we specifically choose Fe-rich Fe58Pt42 , which may
emu/cm3兲 and large K u (⬎5⫻107 erg/cm3 ) and, therefore, yield both large H c and high magnetization.
are attractive as permanent magnetic materials. In the past Annealing at higher temperatures leads to the
decades, the hard-magnetic properties of FePt alloys have evaporation/decomposition of the organic surfactant around
been studied extensively,4,5 however, little has been done on each particle and the decrease of interparticle distances. Tun-
nanostructured FePt systems. Recent progress in the synthe- ing of the interparticle distances is realized by carefully con-
sis of FePt nanoparticles6 makes it possible to utilize nano- trolling the self-assembly and annealing conditions, in an
structured FePt for potential permanent magnet applications, attempt to optimize the nanostructures for high (BH) max . In
situ transmission electron microscopy 共TEM兲 studies on the
because chemical methods have the advantages of highly
annealed nanoparticles show no significant aggregation at
controllable particle sizes and morphologies. Here, we report
annealing temperatures T a below 600 °C.8 As seen from Fig.
detailed magnetic studies on FePt nanoparticle assemblies
1共a兲, for a sample annealed at 530 °C, neither the interpar-
produced by solution-phase synthesis and self-assembly, fol-
ticle distances nor the ordering shows much change com-
lowed by thermal treatment. We find that the thermal treat-
pared to as-deposited samples. At 600 °C or slightly above,
ment controls not only the formation of the high anisotropy
particles start to aggregate 关Fig. 1共b兲兴. However, detailed
L 10 FePt phase but also the interparticle exchange of the
high-resolution TEM 共HRTEM兲 studies 关see the inset of Fig.
1共b兲兴 show that the coalesced particles do not form single-
The high-temperature solution phase decomposition of
crystal agglomerates; instead, two originally separated par-
Fe(CO) 5 and reduction of Pt(acac) 2 produces monodis-
ticles form a twin structure with the grain boundaries being
persed FePt nanoparticles with the composition controlled by easily visible. There is no evidence of carbon residue present
the molar ratio of Fe(CO) 5 and Pt(acac) 2 . 6,7 Deposition of at the grain boundaries, as opposed to previous results on
nanoparticle dispersion on a solid substrate and controlling samples annealed at low temperatures under N2 . 6 It is ex-
solvent evaporation lead to FePt nanoparticle assemblies. pected that even higher temperatures will eventually lead to
The structural properties were characterized by transmission significant agglomerations and the formation of continuous
Electronic mail: Chemically ordered fct FePt nanoparticles may show

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2584 Appl. Phys. Lett., Vol. 80, No. 14, 8 April 2002 Zeng et al.

FIG. 3. ␦ M curves for samples annealed at 550, 600, and 700 °C, respec-

T a results in dramatic changes in interparticle interactions.

Figure 3 shows ␦ M curves for T a ⫽550, 600, and 700 °C,
respectively. ␦ M is defined as M d ⫺(1⫺2M r ), where M d is
the reduced dc demagnetization remanence curve, and M r
the reduced isothermal remanence curve. The ␦ M parameter
has been used to characterize interparticle interactions in par-
ticulate systems.9 It can be seen from Fig. 3 that for T a
⫽550 °C, ␦ M shows a negative peak, indicating that the
predominant interparticle interactions are dipolar. This is
consistent with the TEM observation that all of the particles
are well separated at this annealing temperature. For T a
⫽700 °C, however, the ␦ M curve shows a large positive
FIG. 1. TEM image of 4 nm FePt nanoparticle assemblies after annealing to peak, indicating strong exchange coupling. ␦ M shows a
共a兲 530 °C and 共b兲 600 °C, the inset is the HRTEM of two aggregated FePt small positive peak for T a ⫽600 °C, where particles just start
to touch each other and common grain boundaries are ob-
served 关Fig. 1共b兲兴.
large coercivity originating from their large K u . 4 The degree The initial magnetization curves and hysteresis loops are
of ordering depends strongly on the annealing temperatures. shown in Fig. 4. It is seen that for the sample annealed at
Figure 2 shows the room-temperature H c as a function of 550 °C, which consists of well-separated particles, the rema-
T a , with the annealing time fixed as 1 h. H c first increases nence ratio is 0.55. This is close to the value of 0.5 predicted
rapidly as T a increases from 500 to 600 °C, and then de- for randomly oriented, noninteracting Stoner–Wohlfarth par-
creases dramatically with further increasing T a . A peak ticles. The random orientation together with weak interpar-
value of H c ⬃20 kOe appears at 600 °C. The rising of H c ticle interactions leads to a broad switching field distribution
with increasing T a below 600 °C is mainly due to the im- 共SFD兲. Additionally, the anisotropy distribution may also
provement of the chemical ordering of the FePt particles, contribute to the broadening of the SFD. In a previous work,
leading to the increase of K u . The decrease of H c above physically monodispersed cobalt nanoparticle assemblies
600 °C is very interesting and will be discussed below. 共3–5 nm兲 also show wider than expected anisotropy distri-
The reduction of interparticle distances with increasing bution due to the internal structure, shape, and surface atom
effects.10 For T a ⫽600 °C, the hysteresis loops show a much
higher remanence ratio, and the slope near coercivity is
much steeper. This cooperative switching behavior again in-
fers that the dominant interparticle interaction is exchange
The degree of particle aggregation and changes in inter-
particle interactions also result in different magnetization re-
versal behaviors. As seen in Fig. 4, for T a at or below
600 °C, the initial magnetization curves resemble that for
magnetization rotation of individual particles,12 which is
consistent with weak interparticle interactions. For T a
⫽800 °C, however, the initial curve rises steeply at small
fields and tends to saturate at lower fields, as compared to the
previous samples. This suggests that for the samples an-
FIG. 2. Coercivity H c as a function of the annealing temperature T a , withnealed at higher temperatures, the magnetization reversal
the annealing time fixed to be 1 h. mechanism is controlled mainly by domain nucleation pro-
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Appl. Phys. Lett., Vol. 80, No. 14, 8 April 2002 Zeng et al. 2585

FIG. 5. Coercivity as a function of temperature for samples annealed at 共a兲

550 °C, and 共b兲 800 °C, respectively.

within the nanoparticles are present. For T a ⫽800 °C, H c

shows much weaker temperature dependence, especially at
low temperatures. This suggests that highly exchange-
coupled polycrystalline films show much less thermal ef-
fects, and the temperature dependence of H c most probably
originates from the temperature dependence of K u .
Our results show that optimal magnetic hardening is
achieved in the highly chemically ordered FePt nanoparticles
through proper heat treatments. In such a magnetic nanopar-
ticle assembly, the magnetization rotation of individual par-
ticles yields high coercivity. The interparticle exchange cou-
FIG. 4. Initial magnetization curves and hysteresis loops for samples an-
pling caused by moderate aggregation of particles is
nealed at 共a兲 550 °C, 共b兲 600 °C, and 共c兲 800 °C, respectively.
adequate to give a high remanence ratio and coercive square-
ness, which is mandatory for permanent magnet applications.
cesses. The particle agglomeration leads to the formation of However, excessive exchange coupling leads to the decrease
polycrystalline films, which gives more chances for nucle- of the coercivity.
ation of reversed domains. The decrease of H c at T a above
600 °C may partly be attributed to the change in reversal The authors would like to thank G. Held and E. E. Ful-
mechanisms. Another important factor in reducing H c is the lerton for the critical reading of the manuscript and helpful
random anisotropy effects 共RAE兲.13 As the particle radius discussions. This work is supported in part by U.S. DoD/
becomes smaller than the domain-wall width parameter ␦ w DARPA through ARO under Grant No. DAAD 19-01-1-
⫽(A/K 1 ) 1/2, which is about 2– 4 nm depending on the pa- 0546.
rameters chosen, the effective anisotropy is an average over 1
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