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Synthesis of nanomaterials in
microemulsions: formation
mechanisms and growth control
karen perez

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 Current Opinion in Colloid and Interface Science 8 (2003) 137–144

Synthesis of nanomaterials in microemulsions:

formation mechanisms and growth control夞
´
M. Arturo Lopez-Quintela
Department of Physical Chemistry, University of Santiago de Compostela, E-15782 Santiago de Compostela, Spain

Abstract

The evolution of the microemulsion technique in the last years is revised with special emphasis in the mechanisms of control
of particle size, namely the control by the proper microemulsions and the control by the surfactant adsorption (capping). The
kinetics of the particle formation; the possibility of the preparation of coatings, core-shell and ‘onion-like’ structures with a very
precise size control; the use of microemulsions to produce fine ceramics and finally their use in the preparation of superlattices
is addressed.
䊚 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Microemulsions; Nanoparticles; Core-shell nanostructures; Fine ceramics; Superlattices

1. Introduction alcohols, electrolytes, block copolymers and polyelec-

Microemulsions are colloidal ‘nano-dispersions’ of
water in oil (or oil in water) stabilized by a surfactant
film. These thermodynamically stable dispersions can
be considered as truly nanoreactors which can be used
to carry out chemical reactions and, in particular, to
synthesize nanomaterials. The main idea behind this
technique is that by appropriate control of the synthesis
parameters one can use these nanoreactors to produce
tailor-made products down to a nanoscale level with
new and special properties. This is a very expanding
area and we will describe here our particular opinion
about the most important tendencies which are now
growing in this field.
2. Microemulsion technique: theoreticalysimulation
results
The shape (and size) of the dispersed nanodroplets is
mainly governed by the curvature free energy and is
determined by the elastic constant and the curvatures of
the surfactant film w1x. The elasticity of the film depends
not only on the surfactant type and the thermodynamic
conditions, but also on the presence of additives, like
夞 Specially dedicated to Professor Wilhelm Knoche on occasion
of his 65 birthday, from whom I learned 20 years ago what a
microemulsion is.
E-mail address: qfarturo@usc.es (M.A. Lopez-Quintela).
´ kex; concentration of reactants c; reactant excess ratio x;
trolites. In the past, mainly spherical (and in some cases
elongated) nanodroplets have been used to prepare
nanoparticles of different kind of materials and it was
assumed that the size and shape of these nanodroplets
could ‘template’ the synthesis of nanomaterials w2x.
However, one has to take into account the dynamic
nature of the microemulsions. Due to the Brownian
motion these droplets collide forming a fused dimer (or
an encounter pair) and interchange reactants with a rate
constant kex. The above described parameters, which
determine the elasticity of the surfactant film, influence
also the reactant interchange among the nanodroplets.
The interdroplet exchange of the particles growing inside
the droplets is inhibited by the inversion of the film
curvature in the fused dimer which, in turns, depends
on the film flexibility (Fig. 1). All of this has to be
taken into account to understand the particle size control
in microemulsions. Because a lot of parameters with
different influences enter into consideration, in the last
years Monte Carlo simulations have been performed
trying to get some light into the ‘jungle’ of experimental
results. In a series of papers w3–6●●x Tojo et al. devel-
oped further a previous Monte Carlo simulation proce-
dure w7,8x in which the following parameters have
explicitly being included: the film flexibility through a
parameter f proportional to ky3y2 being k the curvature
elastic modulus; the interdroplet exchange rate constant

1359-0294/03/$ - see front matter 䊚 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S1359-0294Ž03.00019-0
138 ´
M.A. Lopez-Quintela / Current Opinion in Colloid and Interface Science 8 (2003) 137–144
Fig. 1. Schematic representation of a fused dimer after a two droplets
collision showing the channel opened in between. The inversion of
the film curvature in this channel is shown.
droplet size R (which is controlled by the ratio ws
wH2Ox y wsurfactantx); volume fraction f; and critical
nucleus n*. Two more aspects were considered in the
simulation, namely, the possibility of autocatalysis of
the reaction by the already formed sub-nanoparticles
(clusters) and the possibility of ripening. Even for a
Monte Carlo study this is a very time consuming task.
Therefore, until now only a restricted parameter space
could be explored assuming that reactions are performed
by mixing two identical microemulsions carrying the
reactants. It turns out that many of the previous ideas
putted forward to explain the experimental results, based
in the well-known bulk nucleation and growth models,
are not longer valid for the particle formation in these
dynamic compartimentalized media. As an example, it
has been experimentally found that particle size decreas-
es when one of the reactants is in excess (x/1). This
has been explained assuming that when x/1 a faster
nucleation takes place and, therefore, the particles
obtained are smaller. However, simulation results w3x
show that, contrary to the behaviour expected in bulk,
the reactant excess hardly influence the nucleation pro-
cess but, on the contrary, it has a great influence on the
growth mechanisms. In these compartimentalized media
growth by ripening is limited by the channel size opened
in the fused dimer whereas growth by autocatalysis is
only limited by the reactant concentration. When xs1
particles can grow larger than the channel size by
autocatalysis. As x increases (or decreases) the contri-
bution of the growth by autocatalysis decreases and the
particle size is reduced. Because growth by ripening is
faster than by autocatalysis the whole process is faster
at high reactant excess, but this is a consequence not a
reason for the observed diminution of the particle size.
This tells us that one has to be careful when applying
bulk ideas to compartimentalized media. Li and Park
w9x developed a similar Monte Carlo simulation but
without including ripening (this is the same as to assume
a very rigid film, small f) and considering that all the
amount of limiting reactant can be interchanged at each
collision (this is the same as to assume a high value of
kex). Assuming very high concentrations these authors
found a bimodal distribution of particle sizes which had
been observed previously in the experiments and it is
referred to in recent reports w10●x. The results agree
with the Monte Carlo simulation results of Tojo et al.
w7x who found a bimodal distribution at high flexibilities,
intermediate values of kex and high concentrations.
Based on simulation results Tojo et al. w7x have reinter-
preted the experimental results obtained by Bagwe and
Khilar w11●x about the effects of kex on the Ag particle
size prepared in different AOT microemulsions. At this
point it should be convenient to highlight some results
obtained from the simulations and put together with
recent experimental results:
(1) Control of particle size by reactant concentration.
The increase of particle size (and polydispersity) by
increasing the concentration is predicted (bimodality is
obtained for rigid films, as it was previously stated).
Experimentally observed in the formation of Cu nano-
particles in SDSyalcohol mEs w12x; zirconia particles in
ArlacelyIPA mEs w13x; CF3 particles in T154 w14x.
(2) Decrease of particle size by increasing the excess
of one of the reactants until a plateau is reached at high
excesses. This has been observed in the formation of Ni
w15x and Pd w16x particles in CTAByalcohol mEs.
(3) Increase of particle size by increasing the surfac-
tant film flexibility. The increase in flexibility can be
achieved by increasing the amount of cosurfactant (alco-
hols), approaching to the microemulsion instability
phase boundaries, changing the droplet size, changing
the chain length of the oil or cosurfactant, etc. Observed
in the formation of Ni and Pd in CTAByalcohol mEs
w15,16x; tungstic acid in TX-100yalcohol mEs w17x;
Cu2wFe(CN)6x AOT mEs w18x; CdS in CTAByalcohol
w19●●x; Rh in CTACyalcohol w20x.
(4) Increase of particle size by increasing the droplet
size. In principle, a linear relationship should be expect-
ed, but one has to consider that, in many cases, because
of the associated increase of the flexibility with droplet
size these two effects are superimposed and a much
larger increase of the particle size is observed, as it was
found, e.g. by Panda et al. w17x and Moulik et al. w18x.
This effect should be less important working with more
rigid surfactant films. So, for example, good linear
correlations between the particle size and the mole ratio
w are reported by Qiu et al. w12x; Althues and Kaskel
w21x and are in agreement with other previous reports
(see e.g. w22x).
It has to be pointed out that all simulations were
performed under the assumption that the chemical reac-
tion used to produce the particles is much faster than
the material interchange, which is the most usual case.
 ´
M.A. Lopez-Quintela / Current Opinion in Colloid and Interface Science 8 (2003) 137–144
In the opposite case, the most simple bulk ideas of
nucleation and growth can be used to explain the
experimental results using a pseudophase reaction mod-
el. This has been carried out, e.g. by Osseo-Asare and
Arriagada w23x to explain the formation of silica particles
in NP-5 mEs.
3. Particle stabilization: surfactant adsorption and
capping
One interesting aspect which should be now consid-
ered is directly related to the particle size control by the
adsorption of surfactants onto the particles. This has
been observed very often in the formation of particles
in mEs (see e.g. w24x). The surfactant adsorption can
stop the growth of the particles inside the microemulsion
droplets. The particle control by surfactant adsorption
can easily be detected by the fact that the particle size
is almost constant and independent of the various para-
meters discussed above which may affect the particle
size. Because the adsorption on catalysts is favoured
this size control by adsorption has been mostly found
in the preparation of catalysts particles in mEs. Indeed,
the paper of Boutonnet et al. w25x, which is often cited
as one of the first examples of preparation of particles
in mEs, reveals that the particle size of Pt, Rh, Pd and
Ir, in the size range 2–5 nm, is almost independent of
the surfactant, water amount and reactant concentration
used in the preparation. This independence of the syn-
thesis parameters has been confirmed in recent papers
w20,26●,27x, although a small dependence, mainly when
alcohols are used as cosurfactants, has been reported
w16,20x which may be attributed to the simultaneous
influence of the flexibility and differences in the surfac-
tant adsorption. Examples of the surfactant adsorption
size control have also been reported for CdS particles
prepared in CTAB mEs w19●●x. In all these cases the use
of microemulsions to control the final size seems not to
be very useful because one could obtain the same results
in bulk using directly ligand or complexing stabilizing
agents. Although the use of ligands to inhibit the particle
growth is a well-known procedure, much older than the
microemulsion technique (see e.g. w28x), the explanation
of this capping control is still not clear. A statistical
thermodynamic formulation was put forward by Leff et
al. w29x a few years ago to explain the size control in
gold nanoparticles synthesized in the presence of an
alkyl thiol in a two phase aqueousyorganic system.
These authors predicted a minimum stable size when
the surfactant is in excess and also that the particle size
increases by decreasing the surfactant concentration.
This can be rationalized assuming that the positive
entropy change due to the adsorption of the surfactant
decreases as the particle radius, R, increases (in a simple
way one could think that a very small particle is like a
1D object and a large particle a 2D one, so that the
139
Fig. 2. Dependence of the adsorption free energy (and its components
TDS and DH) on the particle radius. rcrit represents the minimum
stable critical radius. rA and rB represent the radii of two microemul-
sions (mA and mB) for which a microemulsion controlled or capping
controlled growth mechanism, respectively, is expected.
entropy reduction should be larger for the adsorption
onto a tiny particle, 3D™1D, than onto a bigger particle,
3D™2D). Fig. 2 schematically shows how the Gibbs
energy for the formation of a surfactant capped particle
would change with R. A minimum stable critical radius,
rcrit, can be predicted. In the same figure, it is shown
that when the microemulsion controlled radius, rA, is
smaller than this critical surfactant controlled radius (for
example, in cases where the adsorption enthalpy is
small) the final particle size is microemulsion controlled.
Surfactant control occurs in the opposite case (rB)rc).
The transition from both kind of controls could
explain the tendency to a plateau which has been
observed in some cases for the particle size when the
droplet size is increased (see e.g. w30x). It should be
mentioned here that in mE control processes one can
stop the growth of the nanoparticles inside the droplets
by adding an appropriate capping agent (‘capping con-
trol’) to the microemulsion as has been reported by
Goffredi et al. w31x. In other cases a capping agent is
used to protect the particles against aggregation when
they are aged or separated from the microemulsion (see
e.g. w19●●,32x). It should be interesting to add directly
to the microemulsions a capping agent with functional
properties in order to prepare functionalised particles,
but we are not aware of any result in this direction and
only this has been proved to work by Liao and Chen
w33x through a two step process to produce yeast alcohol
dehydrogenase bound to magnetic nanoparticles.
4. Kinetics of particle formation in microemulsions
No much work has been performed on this very
interesting area. Turco Liveri et al. w34x studied the
formation of ZnS particles in AOT mEs. Following the
evolution of the wavelength at the band maximum,
140 ´
M.A. Lopez-Quintela / Current Opinion in Colloid and Interface Science 8 (2003) 137–144

which is related to the size of the particles, these authors

deduced the following power law behaviour for the time
evolution of particle size: dAt 0.074. They noted that the
power law exponent is much smaller than the one
predicted by the Lifshitz–Slyozov law (1y3). But this
is only a long-time law. At short-times a 1y6 exponent
is expected w35x, which still is much larger than that
observed by Turco Liveri et al. However, one has to
consider that the particles are growing in a restricted
space for which a drastic reduction of the exponent is
expected due to finite size effects as has been found by
Binder and Heermann for a 3D Ising model w36x. This
tells us again that the nucleation and growth processes,
in these restricted geometries, are very different to the
same processes observed in bulk. Differences in the
kinetics depending on the used surfactant were reported
by Ingelsten et al. w26●x. Explanations based on a change
in the exchange rate, differences in the water droplet
environments and differences in the binding possibilities
are discussed. Finally, it is interesting to note that Wu
et al. w37x reported the possibility that the critical
nucleus, n*, may be dependent on the particle compo-
sition. In general, we feel that more experiments should
be done for checking the growth laws and the kinetics
in these compartmentalized media for a better under-
standing of the particle size control in microemulsions.
5. Coatings, core-shell and ‘onion-like’ particles
In our opinion one of the main advantages of the
microemulsion method to prepare nanomaterials, over
other preparation methods, is the ability to control the
formation of different kind of core-shell(s) structures
with sub-nanometric resolution, as it was previously
demonstrated w38–40,6●●x. The procedure used, sche-
matically shown in Fig. 3, consists in a two-step process:
(1) formation of uniform particles (core) with sizes
smaller than the droplet sizes. According to the above
mentioned ideas this can be achieved using low concen-
trations, excess of one of the reactants and rigid films;
(2) adding new reactants for the second reaction (shell).
The firstly produced particles act as nucleation centers
(seeds) for the second reaction. In this case autocatalysis
should be favoured using stoichiometric amounts of
reactants, high concentrations and rigid films w3x. The
layer thickness can be controlled by the reactant con-
centration. Co–Ag and Fe–Cu–Fe nanoparticles with
antiferromagnetic coupling between the Fe layers have
been produced in this way w6●●x. Based on results
obtained for epitaxially grown thin films the antiferro-
magnetic coupling can only be possible if the interme-
diate non-magnetic Cu shell has an f1 nm thickness
with angstrom monodispersity. Although this powerful
potentiality of the technique has not been fully explored,
in the last years some core-shell structures have been
reported: silica-coated iron oxide by Santra et al. w41●x;
Fig. 3. After the formation of nanoparticles inside the microemulsion
droplets (AqB reaction), new reactants (CqD) are introduced into
the microemulsion system producing a layer of the new material. The
initially produced nanoparticles act as nucleation centers for the sec-
ond reaction.
silica coated zinc ferrite w42● x; gold coated FePtx and
CoPtx w43x. In this section one could include also some
efforts which have been carried out about the encapsu-
lation of nanoparticles with polymers either by extract-
ing the particles from the microemulsions w44x or, more
elegantly, by in situ polymerisation as it was reported
for the preparation of BiyPMMA w45x, CdSyPAM nan-
ocomposites w46●x and BaSO4 in polymerized surfactants
w10●x.
6. Better ceramics through microemulsions
In the last years the formation of ceramics via
microemulsion techniques has experienced a fast growth
mainly because of the incorporation of the sol–gel
technology into the microemulsion method (see e.g.
w47x). In this way a much better control of the stoichi-
ometry of the final product (sol–gel advantage) with a
much finer and controllable grain size (microemulsion
advantage) can be achieved. Examples of this interesting
approach can be found in Refs. w21,48,49●●,50–54x.
Reports about the previous developed precipitationy
coprecipitation method in microemulsions can also be
found w55–59●,60,61x. The lack of methods for inhibit-
ing the aggregation and sintering of the produced nan-
oparticles, when they are fired to crystallize, is a serious
drawback which could be solved by the hot-fluid anneal-
ing procedure just developed by Lin et al. w62●●x.
7. 1D, 2D and 3D nanoparticle superlattices
This is a very fascinating area which began in the
1990s (see e.g. w28,63x) and is now emerging with
enormous potentialities because of their possible and
 ´
M.A. Lopez-Quintela / Current Opinion in Colloid and Interface Science 8 (2003) 137–144
multiple applications in the future nanotechnologies.
Superlattices are made from highly monodispersed nan-
oparticles and are of special interest because they com-
bine the unusual properties of the individual
nanoparticles with collective effects. Although this is
totally away from the scope of this article because
superlattices can be made with other techniques different
from the microemulsion ones (see e.g. w64x), we want
to recall the attention of the reader to some recent results
obtained using microemulsions by the Pileni’s group
w65●●,66–68x. In all of these cases a capping agent is
introduced into the microemulsions, at the end of the
reaction, to achieve a better protection of the particles.
However, the attained monodispersity is not enough and
a selective precipitation size selection was needed to
achieve the particle self-assembly. An interesting
approach combining in one step the nanoparticle synthe-
sis in microemulsions with its self-assembly has also
been reported by Li et al. w69x. Vaucher et al. w70●●x
have also shown that 2D and 3D highly ordered square
(cubic) superlattices can be obtained by a 4 days aging
of a Prussian blue nanoparticle’s microemulsion. One-
dimensional arrangements of nanoparticles prepared in
microemulsions just by aging have also been recently
reported w71,72●,73,74x. No clear reason for this aniso-
tropic growth is known, but it seems that many para-
meters play an important role in the final shape and size
of the observed aggregates, which are very sensitive to
minor changes in the experimental conditions, as it has
been observed in the formation of linear silver aggre-
gates w75x and star-shaped cadmium w76x; but this
extreme sensitivity to the experimental conditions is a
fact which is already very well known in the preparation
of controlled colloidal particles w77x.
8. Conclusions
The microemulsion method is a very versatile tech-
nique which allows the preparation of a great variety of
nanomaterials just alone or in combination with other
techniques. The precise control of all the parameters
which can be varied affecting the final particle sizes
and shapes is still a challenge, but the richness of the
possibilities which can be achieved from nano- to macro-
scales is a big spur to work with these tiny dispersed
droplets, where the only limitation will be our imagi-
nation. Although we have tried to cover the most
important aspects related with this technique, many
items have been left out for discussion, like polymeris-
ation reactions in microemulsions w78●● x, synthesis of
organic nanoparticles w79●●x, industrial uses of mEs
w80,81x, block copolymer mEs w82x and the use of water-
in-supercritical fluid mEs w83x, in particular WyCO2
supercritical mEs w84–86x, which could make this a
more friendly environmental and ‘green’ technique.
141
Acknowledgments
Financial support from the Spanish Ministerio de
´ is gratefully acknowledged (Pro-
Ciencia y Tecnologıa
ject No. MAT2002-00824).
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