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Monodisperse 3d
Transition-Metal
(Co, Ni, Fe)
Nanoparticles and
Their Assembly
into Nanoparticle
Superlattices
C.B. Murray, Shouheng Sun, Hugh Doyle,
and T. Betley
Introduction
Magnetic colloids, or ferrofluids, have
been studied to probe the fundamental
size-dependent properties of magnetic
particles and have been harnessed in a
variety of applications.1–4 The magneto-
rheological properties of magnetic colloids
have been exploited in high-performance
bearings and seals.5 The deposition of mag-
netic dispersions on platters and tapes
marked the earliest embodiments of
magnet information storage.6 Magnetic
particles enhance contrast in magnetic
resonance imaging and promise future di-
agnostic and drug delivery applications.7
The need to explore the scaling limits of
magnetic storage technology has motivated
the preparation of size-tunable mono-
disperse magnetic nanoparticles8–10 with
controlled internal structures. The study
of these nanoparticles is critical to efforts
to separate the role of defects from intrin-
sic, finite size effects.
We report the preparation of colloidal
magnetic nanoparticle samples with con-
trolled size, surface coordination, and
crystallinity that are monodisperse to 1
atomic shell. Figures 1a–d depict the stages
of nanoparticle synthesis, size-selective pre-
MRS BULLETIN/DECEMBER 2001
spins aligned in a single direction.3 Fur-
ther reducing the size of a single-domain
particle decreases the number of spins
exchange-coupled to resist spontaneous
reorientation of its magnetization at a
given temperature. A double-well poten-
tial (Figure 1f) is used to conceptualize the
rotation of the magnetization direction for
a uniaxial magnetic particle.8 The energy
barrier E between the orientations is pro-
portional to the particle volume V and the
material’s anisotropy constant K, which
describes the preference for spins to align
in a particular direction within the particle
due to the influence of crystal symmetry,
shape, and surface effects. As the particle
size decreases, E becomes comparable
to thermal energy (kBT), and the energy
barrier no longer pins the magnetization
on the time scale of observation. The par-
ticle is said to be superparamagnetic.
Mapping the scaling limits of magnetic
storage technology8,9 and understanding
cipitation, self-assembly, and nanoparticle
superlattice formation, respectively. Fig-
ure 1e shows a schematic diagram of a
model nanoparticle with its crystalline
metallic core, oxidized surface, and a mono-
layer coat of organic stabilizers (surfac-
tants). In this article, crystalline particles
with low concentrations of defects are re-
ferred to as nanocrystals (NCs), while the
more general term nanoparticle (NP) will
refer to particles containing gross internal
grain boundaries, fractures, or internal
disorder. Comparing the size evolution of
the magnetic properties in these systems
Figure 1. Schematic representation
reveals the importance of internal crystal of (a) nanoparticle (NP) synthesis by
structure. high-temperature solution-phase routes;
The magnetic properties of nanometer- (b) size-selective precipitation, used to
sized particles arise from the competition narrow NP sample-size distributions;
between strong, short-range exchange inter- (c) self-assembly of NP dispersions;
actions and long-range, dipolar couplings and (d) formation of ordered NP
of electron spins in the atoms that make assemblies (superlattices). (e) Model
up magnetic solids. These competing inter- nanoparticle with its close-packed
actions favor parallel alignment of nearby metallic core, oxidized surface, and a
monolayer coat of organic stabilizers
spins and antiparallel alignment of distant (surfactants). (f) Graph of the energy-
spins, forming magnetic domains in “bulk” dependence of NP magnetization.
magnets.1–3 In a small particle, truncation E represents the energy barrier to the
of the long-range, dipolar forces results in rotation of the magnetization. The left
a “single-domain” magnet with all of the and right arrows represent spin states.
985
 Monodisperse 3d Transition-Metal (Co, Ni, Fe) Nanoparticles
spin-dependent transport phenomena in
nanoscale devices11 motivate studies of mag-
netic NPs.
General Synthesis of
Monodisperse 3d Transition-Metal
Nanoparticles
One general scheme for preparing
monodisperse (standard deviation s , 5%)
3d transition-metal NPs relies on producing
a single short nucleation event followed
by slower growth on the nuclei formed.12–15
This is achieved by either injecting a re-
ducing agent into a hot solution of metal
precursors and surfactants, or injecting
thermally unstable, zero-valent metal pre-
cursors into a hot solution containing col-
loidal stabilizers (Figure1a). Adjusting the
temperature and the metal-precursor-to-
surfactant ratio controls NP size. Higher
temperatures and larger metal-precursor-
to-surfactant ratios produce larger NPs.
Surfactants adsorb reversibly to NP sur-
faces, providing a dynamic organic shell
that mediates growth, stabilizes the NPs
in solution, and limits oxidation after syn-
thesis. An effective strategy employs a pair
of surfactants, where one binds tightly
to the metal NP surface (e.g., oleic acid),
favoring slow growth, and the other binds
weakly, permitting rapid growth (e.g., tri-
octylphosphine, TOP, and tributylphos-
phine, TBP).12– 15 The ratio of the strongly
and weakly binding surfactants is adjusted
to control NP size. Surfactants with simi-
lar binding chemistry, but with greater
steric bulk (bulky TOP instead of TBP)
slow NP growth, reducing the average
NPsize.
Although weakly binding surfactants
are important in mediating growth, ele-
mental analysis indicates that only the
strongly binding surfactant remains co-
ordinated to the surface of 3d transition-
metal NPs when isolated from the growth
solution. The surfactant can be exchanged
for surfactants of different length or chemi-
cal functionality. Adding a large excess of
a substitute surfactant to a NP dispersion
and heating and stirring the solution are
generally sufficient to exchange the ma-
jority of the stabilizers. NPs can be re-
extracted, and repeating the procedure
increases the fraction exchanged.14
Colloidal synthesis can yield mono-
disperse NPs directly from the growth
solution,15–17 but generally an initial size
distribution of s , 7–10% is considered
a success. Size-selective precipitation is
used to narrow the NPsize distribution. A
nonsolvent miscible solution with the dis-
persing solvent is added dropwise, gradu-
ally destabilizing the dispersion until a
slight cloudiness is apparent. The disper-
sion is centrifuged, yielding a small amount
986
of precipitate enriched in the largest NPs,
which is discarded. The supernatant solu-
tion, containing the majority of the NPs, is
decanted, and more nonsolvent is added
dropwise while stirring until a dense,
cloudy suspension is formed. Centrifug-
ing isolates most of the NPs in the pre-
cipitate, leaving the smallest NPs and
synthetic by-products in the supernatant
solution, which is discarded. At this stage,
the precipitate generally exhibits a near-
Gaussian size distribution (s , 7%). Size-
selective precipitation of magnetic NPs is
enhanced by magnetic fields (e.g., holding
a strong magnet next to the centrifuge
tube or using a magnetic stirrer), as the
larger magnetic NPs are more effectively
separated and retained in the precipitate.
The size distribution is further narrowed
(s , 5%) by redispersing the NPs in fresh
solvent with ,0.1% stabilizer added to
maintain a stable colloid and repeating the
procedure.
Synthesis of Monodisperse
hcp Cobalt Nanocrystals
Reduction of cobalt salts by polyalcohols
(polyols) at temperatures between 1008C
and 3008C in the presence of stabilizers
produces Co NPs with diameters of
2–20 nm.18 We find that using long-chain
1,2-diols instead of commonly used ethyl-
ene glycol or glycerol reducing agents has
an advantage; the precursors and NPs
remain well dispersed during growth,
avoiding the formation of insoluble pow-
ders that preclude size-selective precipita-
tion.19 We report the synthesis of Co NCs
with a predominantly hcp internal crystal
structure.
In a typical synthesis of 6–8-nm hcp Co
NCs, 1.0 g (4mmol) of Co(CH3COO)2 ? 4H2O
is combined with 1.28 ml (4mmol) of oleic
acid in a flask with 40 ml of diphenylether
(DPE) and heated to 2008C under N2. One
can substitute dioctylether for DPE in any
of the following procedures, but it is sig-
nificantly more costly. When the reaction
reaches 2008C, ,2.0 mmol TOP is added,
and the mixture is heated to 2508C. In a
separate flask, 2.1 g of 1,2-dodecanediol is
dissolved in 10 ml of dry DPE. The reduc-
ing solution is heated to 808C under vac-
uum for 15 min, back-flushed with N2,
and injected into the hot (2508C) reaction
vessel. The solution changes color from
blue to black over a period of 2 min as the
Co NCs nucleate and begin to grow. The
reaction is held at 2508C for ,15–20 min,
consuming the reagents. The Co NC dis-
persion is cooled, and the NCs are isolated
by size-selective precipitation. NC size
is tuned by tailoring the concentration or
composition of stabilizers: increasing the
concentration of oleic acid and TOP by
a factor of 2 yields smaller, 3–6-nm NCs,
while substituting TBP for TOP forms
larger, 10–13-nm Co NCs.
A transmission electron microscope
(TEM) image (Figure2a) of a large ensem-
ble of 6-nm hcp Co NCs (s , 5%) shows
uniform NCs assembling into a super-
lattice. High-resolution TEM (HRTEM) (Fig-
ure 2b) reveals a crystalline core with a
lattice spacing of ,2 Å. A series of TEM
images are analyzed to develop a statisti-
cal model of the NC sample size, size dis-
tribution, shape, and frequency and mode
of defects (stacking faults along the c axis
in hcp NCs are the predominant source of
disorder).
An atomistic model of the NC ensemble
is built using collections of atomic coordi-
nates to represent the atoms in the NCs.
The atomic coordinates for a series of NC
sizes are input into a discrete form of the
Debye equation, and a weighted sum is
taken to simulate the wide-angle x-ray
scattering (WAXS) of NC ensembles with
a specific size and size distribution.14,20
Stacking faults are introduced in model
NCs by assigning a faulting probability as
the atomic coordinates are generated. The
parameters of size, size distribution, shape,
and defect density are refined to provide
the best simultaneous fit to the experi-
mental diffraction and TEM results. Fig-
ure 2c shows the WAXS pattern for a
sample of 8-nm hcp Co NCs (open circles)
and the corresponding computer simula-
tion (solid line). Patterns and simulations
for 4-, 6-, 8-, and 10-nm samples are
shown in Figure 2d. Finite size effects
broaden each x-ray reflection, and in hcp
Co NC samples, the (100), (102), and (103)
reflections are further broadened and at-
tenuated by stacking faults along the [002]
direction that introduce the fcc character.
Fits are consistent with 70–80% hcp and
20–30% fcc characters in each NC.
Substituting 4.0mmol of Ni(CH3COO)2 ?
4H20 for the Co precursor and using a
mixture of 2 mmol of oleic acid, 1 mmol
of TBP, and 8 mmol of tributylamine
(TBA) stabilizers in the procedure yields
12–13-nm Ni NPs. Replacing TBP and
TBA with TOP and trioctylamine (TOA),
respectively, produces 8–10-nm Ni NPs
with even smaller NPs synthesized by in-
creasing the amount of oleic acid. Co/Ni
alloys are prepared using a mixture of
Co(CH3COO)2 ? 4H2O and Ni(CH3COO)2 ?
4H2O. Figure3a shows a low-magnification
TEM image of an ensemble of 8-nm
Co/Ni alloy NPs (s ­ 5%). Although equal
amounts of Co and Ni precursors were
employed, energy-dispersive x-ray spec-
troscopy reveals that the NPs are 40% Co
and 60% Ni, indicating Ni is more readily
incorporated into the growing NPs. The
MRS BULLETIN/DECEMBER 2001
 Monodisperse 3d Transition-Metal (Co, Ni, Fe) Nanoparticles

Figure 3. (a) Low-magnification TEM image of 8-nm Co/Ni alloy

Figure 2. (a) Low-magnification transmission electron microscope
(TEM) image of a large ensemble of 6-nm hcp Co nanocrystals
(NCs) packing into an ordered superlattice. (b) High-resolution
TEM (HRTEM) image of a 7-nm hcp Co NC. (c) Wide-angle x-ray
scattering (WAXS) pattern of 8-nm hcp Co NCs (open circles)
and computer simulation (solid line) generated from TEM
measurements of sample size, internal structure, and shape;
(d) inset shows the WAXS patterns for 4-, 6-, 8-, and 10-nm hcp
Co NCs with their respective fits.
NPs; (b) inset shows an electron-diffraction pattern from an
8-nm Co/Ni NP sample, confirming the predominantly fcc
structure. (c) TEM image of an ensemble of 8-nm multi-twinned
fcc (mt-fcc) Co NPs; (d) inset shows HRTEM image highlighting
the mt internal structure of the 8-nm mt-fcc NPs. (e) TEM image
of an ensemble of 6-nm Fe NPs; (f) at higher magnification (inset),
the surface oxide layer is clearly visible. (g) Image of an ensemble
of 6-nm FePt NPs; (h) inset shows HRTEM image of a FePt NC
after annealing and forming of the face-centered-tetragonal
(fct) phase.

electron-diffraction pattern (Figure 3b)
shows that this alloy has a predominantly
fcc crystal structure.
Multi-Twinned Co Nanoparticles
One established preparation of Co
NPs employs thermal decomposition of
Co2(CO)8 in the presence of surfactants
under an inert atmosphere.5,21,22 When
air is not excluded from the reaction,
metal-oxide particles are isolated.16,23 These
carbonyl decomposition procedures are
scalable to large quantities for the com-
mercial production of magnetic fluids.5
Carbonyl-based syntheses typically do
not yield single-crystal particles (NCs);
rather, the NCs are comprised of multiple
fragments of the bulk fcc lattice with sev-
eral radial twin planes in each particle.24,25
These multi-twinned (mt) particles are
members of a family of polyhedral struc-
tures and have been studied in several
transition-metal systems.26,27 We adopt the
label mt-fcc Co NPs for these samples.
While we describe the synthesis of mt-fcc
Co NPs, a recent work reports the synthe-
sis of crystalline samples using carbonyl
precursors.28
To synthesize 8–10-nm mt-fcc Co NPs,
a reaction vessel with 40 ml of DPE is
heated under N2 to 200C, and 2.0 mmol
(0.64 ml) of oleic acid and 2.0 mmol of TBP
are added. In a separate flask, 684 mg of
Co2(CO)8 is combined with 10 ml of dry
DPE, warmed briefly to 40–60C under N2
until fully dissolved, and then rapidly
injected into the reaction vessel. The solu-
tion turns black and foams as Co2(CO)8
decomposes, nucleating Co NPs and re-
leasing CO gas. The vessel is held at
200C for 15–20 min, allowing the NPs
to grow. The solution is cooled, and the
NPs are isolated by size-selective precipi-
tation. Figure 3c shows 8-nm mt-fcc Co
NPs, and a higher-magnification image of
the same sample (Figure 3d) highlights
the presence of radial twin planes.
Fe NPs are prepared by replacing
Co2(CO)8 with Fe(CO)5 in the described
procedure and carrying out the growth at
250C.5 After injection of a yellow-brown
Fe(CO)5 solution, the reaction rapidly
turns from brown to black and foams as
CO is released and Fe NPs nucleate. The
Fe NPs are sensitive to oxidation, and thus
size-selective precipitation is carried out
under N2. The Fe NPs (Figure 3e) have a
structure resembling the bulk bcc lattice,
but show evidence of disorder and have
a 2-nm-thick oxide shell (Figure 3f).
Alloys of Fe and Co are accessible using
a mixture of Co2(CO)8 and Fe(CO)5 at
250C, although the isolated NPs are poorly
crystallized.
Alloys and intermetallic phases are
produced when 3d transition metals such
as Fe are combined with Pt. Sun et al.
have reported the preparation of 3–10-nm
FePt NPs (  5%) by reduction of
Pt[CH3COCHC(O)CH3]2 and decompo-
sition of Fe(CO)5 in the presence of oleic
acid and oleylamine stabilizers.10,17 Each
NP consists of a disordered Fe/Pt fcc core
and a surface coordinated by both amine
and carboxylate stabilizers, which are re-
tained when the NPs are isolated. These
alloy NPs are converted to ordered face-
centered-tetragonal (fct) NCs upon an-
nealing to temperatures 550C. The
high magnetocrystalline anisotropy of
this intermetallic phase allows NCs as
small as 3.5 nm to display strong, room-
temperature ferromagnetism,10,17 making
these phases interesting for future mag-

MRS BULLETIN/DECEMBER 2001 987

 Monodisperse 3d Transition-Metal (Co, Ni, Fe) Nanoparticles

netic media.9 An ordered assembly of un-

annealed 6-nm FePt NPs (Figure 3g) with
a 1-nm NP spacing has been produced by
exchanging the original oleic acid and
oleylamine stabilizers with hexanoic acid
and hexylamine. An HRTEM image (Fig-
ure 3h) of an annealed 4-nm FePt NC
shows lattice fringes due to the alternating
planes of Fe and Pt.17

-Cobalt Nanocrystals
Several synthetic routes yield Co NCs
having a third distinct crystal structure,
called -cobalt.12,13,19,24 The -cobalt crystal
structure consists of a complex, 20-atom
unit cell (isomorphic with the  phase
of Mn) that does not favor the formation
of low-energy stacking faults as does the
hcp/fcc system. The -Co NCs are con-
verted to hcp and fcc Co by annealing
at temperatures of 300C and 500C,
respectively.12,13 Magnetic measurements
[ferromagnetic resonance and super-
conducting quantum interference device
(SQUID) magnetometry], TEM, and WAXS
studies have been combined with com-
puter simulations for mt-fcc Co NPs
and -Co NCs.29 Comparison of the size-
dependent magnetic properties of hcp Co
NCs, mt-fcc Co NPs, and -Co NC
samples provides an opportunity to ob-
serve the effects of internal crystal struc-
ture in a single elemental system.

Magnetic Properties
of Nanoparticles
Each NP (Co, Ni, Fe, or alloy) is a single-
domain magnet, as described earlier. The
magnetization M of an ensemble of non-
interacting, single-domain NPs decays
after removing a saturating field as
M(t) e
t/, where   f
1
0 e
kv/kBT
and f0 (the
attempt frequency) is 109–1011 Hz.3 To in-
vestigate the magnetic properties inherent
in independent NPs, the NP samples must
be monodisperse and the particle inter- Figure 4. (a) Magnetization versus applied-field hysteresis (M versus H) loops at 5 K for
actions must be minimized.29,30 In our 3-, 6-, 8-, and 11-nm hcp Co NC samples. (b) Comparison of M versus H loops for 9.5-nm
experiments, the oleic-acid-stabilized par- -Co NCs at 5, 40, 100, and 300 K. (c) A series of zero-field-cooled (ZFC) and field-cooled
(FC) magnetization scans for hcp Co NC samples (3, 6, 8, and 11 nm). (d) Plots of Hc versus
ticles are dispersed at   0.5% by weight
particle diameter for a collection of hcp Co, -Co, and mt-fcc Co samples.
in paraffin or polyvinyl pyrrolidone. The
coercivity Hc, the field required to reverse
the magnetization, decreases with de- leading to superparamagnetic behavior become unpinned and align with the
creasing NC size, as seen in M versus H above the blocking temperature TB, where applied field, increasing the sample’s net
loops measured at 5 K (Figure 4a) for a se- hysteresis drops to zero.4 This 9.5-nm magnetization. At TB, the thermal energy
ries of hcp Co NC sizes.25 The sharp drop -Co NC sample is superparamagnetic causes the NC moments to begin to fluc-
in saturation magnetization (relative to above 125 K. A series of zero-field-cooled tuate in the small field, reducing the net
that for bulk Co) with decreasing NP size (ZFC) and field-cooled (FC) scans are magnetization. In FC scans, samples are
results from the increase in the NP shown in Figure 4c, in which magnetiza- cooled in a small field (10 Oe), freezing-in
surface-to-volume ratio and the presence tion is measured as a function of tempera- a net alignment of the NC moments. The
of 1–2 monolayers of cobalt oxide.31 ture for several sizes of hcp Co NCs. In field is removed, and the magnetization
In Figure 4b, a temperature series of M ZFC scans, a sample is cooled in zero is measured as the sample is slowly
versus H loops for a dispersion of 9.5-nm applied field, and the magnetization is warmed. Thermal energy unpins and ran-
-Co NCs is displayed. Increasing thermal recorded as the temperature is increased domizes the NC moments, lowering the
energy helps the NCs reorient with the in the presence of a small field (10 Oe). As sample’s net magnetization. At TB, the
applied field H, reducing hysteresis and the thermal energy increases, the NCs ZFC and FC curves converge.32

988 MRS BULLETIN/DECEMBER 2001

 Monodisperse 3d Transition-Metal (Co, Ni, Fe) Nanoparticles

In magnetic recording, the remanent

magnetization Mr of the grains (in this
case, NCs) encodes the information. Thus,
the stability of magnetic information has a
double exponential dependence on K and
V, leading to an extraordinarily steep drop
in thermal stability at nanometer sizes.8 A
plot of coercivity Hc versus NC diameter
(Figure 4d) summarizes 5 K hysteresis
loops measured for several sizes of hcp
Co, mt-fcc Co, and -Co. The Hc of the
smallest NPs is dominated by coupling to
the surface CoO layer. For each system, Hc
is lower than that predicted for idealized
NPs, as internal structural defects (stack-
ing faults, twinned planes) reduce Hc.
While 3d transition-metal NPs provide
model systems for studying the size-
dependent stability of magnetic media,
magnetic NP superlattices (described in
the next section) are also being investi-
gated as model granular magnetoresistive
materials.11 Future ultrahigh-density re-
cording media will require uniform par-
ticles (  10%) with an average diameter
of 6 nm and a room-temperature Hc of
3000–5000 Oe. Although the Hc of elemen-
tal Co is too low for advanced media,
we have extended this synthetic approach
to prepare ordered arrays of higher-
coercivity intermetallic NCs such as FePt
(Figures 3g and 3h).17
Magnetic NP Superlattices
Colloidal NPs self-assemble from solu-
tion, forming close-packed NP arrays on a
variety of substrates as the dispersing sol-
vent evaporates. Tailoring the composition
and combination of dispersing solvents
and the temperature during deposition
induces assembly of close-packed glassy
films or ordered NP superlattices. Prepar-
ing samples with narrow size distributions
is critical to achieving long-range order in
NP assemblies: for size distributions of
  7%, short- to medium-range order is
observed; reducing  to 5% enables the
formation of assemblies with long-range
order, known as colloidal crystals or super-
lattices.14,33–35 However, even a sample with
  5% can yield close-packed glassy NP
films having only short-range order if the
deposition conditions are not appropri-
ately tailored and the evaporation rate is
too high.14 Figure 5a shows an ensemble
of 9-nm Ni NPs that has been deposited
onto an amorphous carbon TEM grid from
Figure 5. (a) TEM image of a close-packed glassy film of 9-nm Ni NPs deposited onto
an amorphous carbon TEM grid from pentane; the higher-magnification inset shows a
degree of local order. (b) TEM image of a 9-nm Ni NP superlattice grown by slow drying of
a hexane/octane dispersion; the inset shows that ordering has improved. (c) WAXS pattern
for a 9-nm Ni NP sample. (d) Small-angle x-ray scattering (SAXS) patterns for 9-nm NPs:
(curve A) dispersed at 1% by weight in poly(vinyl butyral), (curve B) deposited as a glassy
film from pentane, (curve C) deposited over 5 min from hexane/octane, and (curve D)
covered and dried slowly from hexane/octane over a period of 40 min. (e) ZFC-FC scans
from 9-nm Ni NPs: (curve A) dispersed, (curve B) in a superlattice, and (curve C) in a
superlattice annealed under vacuum.
able lattice sites in a growing assembly.14 over 5 min from hexane/octane; and in
Ordering is improved, as seen in Figure 5b curve D, the film has been covered, ex-
for a Ni NP superlattice, by covering the tending the drying time to 40 min. With
substrate and further lowering the evapo- increasing drying time, the Bragg reflec-
ration rate. The inset in Figure 5b shows a tions from the hexagonally packed sheets
higher-magnification image. of NPs become sharper and more in-
Figure 5c shows a WAXS pattern for the tense.14,34 The reflections correspond to 9-nm
9-nm Ni NP sample, confirming the pre- NPs separated by a 4-nm surfactant layer.
dominantly fcc crystal structure of the in- In Figure 5e, the ZFC-FC scans for (curve
dividual NPs. A series of small-angle x-ray A) dispersed Ni NPs and (curve B) close-
scattering (SAXS) patterns following the packed assemblies show that TB shifts and
development of ordering is seen in Fig- broadens as dipolar coupling between
pentane. Rapid drying (10 s) has frus-
trated the formation of long-range order.
The higher-magnification image (inset in
Figure 5a) shows a degree of local order.
Depositing the same sample of Ni NPs
from 80% hexane and 20% octane slows
the evaporation rate (5 min) and gives
the NPs time to find energetically favor-
MRS BULLETIN/DECEMBER 2001
ure 5d. The SAXS pattern (curve A in Fig-
ure 5d) of 9-nm NPs dispersed at 1% by
weight in a poly(vinyl butyral) matrix
shows the oscillations characteristic of the
NP size and size distribution.14,34 Curve B
in Figure 5d shows scattering from a glassy
film deposited from pentane; curve C
shows scattering from a film deposited
NPs increases. As the sample is annealed
under vacuum (curve C), TB continues to
shift as the surfactant is partially desorbed,
and the interparticle distance decreases
to 2 nm.13,33
The wetting properties of the substrate
influence the NP superlattice morphology.
If the NP dispersion wets the substrate,
989
 Monodisperse 3d Transition-Metal (Co, Ni, Fe) Nanoparticles

the superlattice growth is more two-
dimensional, first forming a monolayer and
then multilayers as coverage increases. NPs
adsorb to ledges and kinks of the growing
structures, forming terraces that extend
laterally across the substrate. A step-like
structure is seen in the scanning electron
micrograph (Figure 6a) at the edge of a
10-nm mt-fcc Co NP superlattice grown
on a hydrofluoric-acid-dipped silicon wafer.
Figure 6 shows the large central terrace of
this same superlattice domain.
If the NP dispersion does not wet the
substrate, superlattice growth is more
three-dimensional, forming facets that re-
flect the packing symmetry of the NPs.
Figure 7a shows a TEM image of a hexago-
nal superlattice with rows of 8-nm mt-fcc
Co NPs aligning to form facets. An image
of a larger hexagonal superlattice (col-
loidal crystal) is seen in Figure 7b.14 When
a magnetic field of 1000 Oe is applied in
the plane of the substrate during deposi-
tion of this same NP dispersion, the super-
lattice morphology changes markedly.25,33
Spindle-shaped deposits grow with their
long axes aligned with the field. Fig-
ures 7c–7e show this sample at increasing
magnifications. Deposition in a magnetic
field introduces anisotropy in the assem-
bly and thus in magnetic properties of the
NP films.
Conclusions
High-temperature, solution-phase syn-
theses yield Co, Ni, Fe, and alloy nano-
particle samples that are uniform in size
(to 1 atomic layer), composition, shape,
internal structure, and surface chemistry,
allowing the properties of nanoscale mag-
netic materials to be mapped. These nano-
particles constitute a versatile new set of
nanoscale building blocks with which to
assemble magnetic materials and devices.
Under controlled deposition conditions,
these nanoparticles self-assemble from so-
lutions to form glassy close-packed solids,
extended two- and three-dimensional
superlattice films, and faceted colloidal
crystals. The resulting magnetic nano-
particle assemblies provide model sys-
tems with which to explore collective
interparticle interactions (e.g., dipolar, ex-
change, spin-dependent tunneling) that
are critical to the optimization of future
magnetic technologies.
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a review, see J.L. Dormann, D. Fiorani, and
E. Tronc, Adv. Chem. Phys. 98 (1997) p. 283; K.
O’Grady, R.W. Chantrell, Magnetic Properties of
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Figure 6. (a) High-resolution scanning

electron microscope (HRSEM) image
showing the 10-nm mt-fcc Co NPs
forming ledges at the edge of a
superlattice; inset shows the ledges
at higher magnification. (b) HRSEM
image of the top surface of the NP Figure 7. (a) TEM image of a hexagonal superlattice grown from 8-nm mt-fcc Co NPs with
superlattice imaged in 6a; inset shows no applied magnetic field. (b) Lower-magnification image of large hexagons formed in the
higher-magnification image of the sample. (c)–(e) Images at increasing magnification of spindle-shaped superlattices grown
same sample. with a 1000-Oe field applied in the plane of the substrate.

990 MRS BULLETIN/DECEMBER 2001

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