Materials Today  Volume 16, Numbers 7/8  July/August 2013 RESEARCH

RESEARCH: Review

The fascinating world of nanoparticle

research
Florian J. Heiligtag and Markus Niederberger*
Laboratory for Multifunctional Materials, Department of Materials, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093 Zurich, Switzerland

Nanoparticle research is a fascinating branch of science. The strongly size-related properties of

nanoparticles offer uncountable opportunities for surprising discoveries. The often unexpected and
unprecedented behavior of nanoparticles bears great potential for innovative technological
applications, but also poses great challenges to the scientists. They have to develop highly controllable
synthesis approaches, more sensitive characterization tools and finally new models and theories to
explain the experimental observations. In this review, we discuss a personal selection of papers
dedicated to nanoparticle research, which we believe provide an illustrative overview of current research
directions in this rapidly developing field. We have structured the text in five sections: introduction,
nanoparticle synthesis, formation mechanisms, nanoparticle assembly, and applications. The chosen
examples within these sections are not directly related to each other, but reflect the remarkable
broadness of nanoparticle research covering historical aspects, basic and applied science as well as
commercial applications.

Introduction outermost layers of the glaze [6]. The example in Fig. 1a displays
Nanoparticles have a surprisingly long history. Their preparation is iridescence under specular reflection with shiny blue and green
neither an exclusive result of modern research nor restricted to colors. Transmission electron microscopy (TEM) analysis revealed
man-made materials. Naturally occurring nanoparticles include a double layer of silver nanoparticles with smaller sizes (5–10 nm)
organic (proteins, polysaccharides, viruses, among others) as well in the outer layer and larger ones (5–20 nm) in the inner layer
as inorganic compounds (iron oxyhydroxides, aluminosilicates, (Fig. 1b). The distance between the two layers is constant at about
metals, among others) and are produced by weathering, volcano 430 nm, giving rise to interference effects (Fig. 1c) [6]. The light
eruptions, wildfires or microbial processes [1,2]. Nanoparticles are scattered by the second layer has a phase shift with respect to the
not necessarily produced by modern synthesis laboratories, but one scattered by the first layer, and because the phase shift
have obviously existed in nature for a long time, and therefore depends on the wavelength of the incoming light, each wave-
their use can be traced back to ancient times. While the application length is scattered differently.
of clay minerals as natural nanomaterials does not seem to be very Metal nanoparticles are able to color glass in an extraordinary
sophisticated, the controlled reinforcement of a ceramic matrix way. Gold has been used for a long time to introduce a striking red
with natural asbestos nanofibers more than 4500 years ago is more color to glass. One of the finest examples of such ruby glass is the
intriguing [3]. However, the most spectacular effects were obtained Lycurgus Cup in the British Museum (Fig. 2a). Manufactured by
with metal nanoparticles as color pigments in luster and glass Romans in the fourth century it appears with a green color in
technology [4,5]. Metallic luster decorations of glazed ceramics daylight (Fig. 2a, left), but changes to red (Fig. 2a, right), when
appeared in Mesopotamia during the 9th century [6]. These dec- illuminated from the inside [7,8]. An interesting fact about the use
orations showed amazing optical properties due to the presence of of gold nanoparticles in ruby glass is that after the Romans the
separate silver and/or copper nanoparticles dispersed within the technology was forgotten, and was only rediscovered in Europe
in the seventeenth century. Although the birth of gold-based
*Corresponding author:. Niederberger, M. ([email protected]) glass and enamel colors is ascribed to Andreas Cassius, who

262 1369-7021/06 ß 2013 Elsevier Ltd. Open access under CC BY-NC-ND license. http://dx.doi.org/10.1016/j.mattod.2013.07.004
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RESEARCH: Review
FIGURE 1
(a) Photograph of a medieval piece of a glazed ceramic observed by scattered light and specular reflection. (b) TEM image of the double layer of silver
nanoparticles. (c) Schematic representation of interference phenomena due to the double layer. Reproduced from Ref. [6] with permission of Trans Tech
Publications and Dr. Philippe Sciau.

subsequently received the name Purple of Cassius, the preparation time the bright yellow color of the Na[AuCl4] solution turned into
of colloidal gold with a tin compound had been described several a ruby color characteristic of gold nanoparticles (Fig. 2c).
years earlier by Johann Rudolph Glauber [9]. However, there is no The principle motivation to perform research on nanoparticles
evidence that Glauber ever applied his knowledge to the coloring is founded in the so-called quantum size effect. Metal and semi-
of glass. It was Johann Kunckel, who ran a glass factory in Potsdam conducting nanoparticles just a few nanometers in diameter, and
between 1679 and 1689, that successfully used the purple pre- thus with sizes somewhere between single atoms/molecules and
cipitate to produce ruby glass (Fig. 2b) [9]. From a scientific point of bulk materials, show pronounced size- (and also shape-) depen-
view, the next big step forward in nanoparticle research was made dent electronic and optical properties [12–14]. The observation of
by Michael Faraday approximately 150 years ago. As a matter of such size effects raised expectations for the superior performance
fact, his systematic studies on the interaction of light with metal of nanomaterials compared to their bulk counterparts in many
nanoparticles can be regarded as the beginning of modern colloid applications, if the size and the shape of the particles can be
chemistry and the emergence of Nanoscience and Nanotechnol- optimized in a rational way. Systematic work on the photocata-
ogy [10]. In 1857 he presented his work on ‘Experimental Relations lytic properties of colloidal CdS [15,16] resulted in the description
of Gold (and other Metals) to Light’ to the Royal Society of London of the quantum size effect at the beginning of the 1980s. Brus et al.
[11]. Faraday prepared his colloidal gold dispersions in a two-phase found that CdS crystallites in the size range of a few nanometers
system consisting of an aqueous solution of a gold salt and a did not have the electronic spectra of the bulk material, even
solution of phosphorus in carbon disulfide. After a short reaction though they exhibited the same unit cell and bond length as the

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FIGURE 2
(a) The Lycurgus Cup in reflected (left) and in transmitted (right) light. ß Trustees of the British Museum. (b) Beaker with lid attributed to Johann Kunckel
using the purple preparation of gold chloride and stannous hydroxide later to be associated with the name of Andreas Cassius.
Source: http://de.wikipedia.org/wiki/Johannes_Kunckel. (c) Five original bottled samples prepared by Michael Faraday. Source: http://aveburybooks.com/
faraday/catalog.html. Reprinted with permission of Prof. Ryan D. Tweney (Bowling Green State University) and Prof. Frank James (Royal Institution).

bulk material [17]. These findings opened up a new and exciting When it comes to the synthesis of gold nanoparticles, probably
possibility to tailor the chemical and physical properties of a the most convenient and widely used synthesis technique is the
material: new applications and properties as a result of controlling so-called citrate route developed by Turkevich et al. more than 60
crystallite size and shape on a nanometer scale rather than by years ago [19]. The reaction is very simple and involves just gold
altering the composition [14]. Consequently, the development of chloride, sodium citrate as a reducing and stabilizing agent and
advanced synthesis routes not only offering control over the water as a solvent. The obtained gold nanoparticles exhibit a
composition, as typically required for traditional bulk synthesis, spherical morphology (Fig. 3a) with a relatively narrow size dis-
but also over particle size, size distribution, shape and surface tribution (20  1.5 nm) [19]. Although the citrate route is still very
properties became essential on the way to study and apply the popular for the preparation of aqueous gold nanoparticle sols,
size-dependent properties of nanomaterials. many other approaches have been developed, performed in spe-
cific organic solvents or in the presence of different types of
Nanoparticle synthesis surfactants and reducing agents to fine-tune the morphology from
After several decades of intense research effort, it is apparent that a nanocubes (Fig. 3b) to hexagonal shapes (Fig. 3c), nanorods
large number of synthesis approaches to a great variety of nano- (Fig. 3d) and nanostars (Fig. 3e) [20,21]. Interestingly, all these
particles are available. Here we will exclusively focus on liquid- nanoparticles have different optical properties. In the case of gold
phase routes. In addition, due to space limitations, we restrict the nanorods with varying aspect ratios (Fig. 3f), this effect is visible to
number of the examples to just a few that are representative for a the naked eye [22]. The optical absorption spectra show a shift of
specific class of materials and that are still frequently used. A more the band at longer wavelengths, corresponding to the absorption
comprehensive overview of solution routes to nanoparticles is and scattering of light along the long axis of the nanorods, from
given in Ref. [18]. the visible to near infrared with increasing lengths, and the color

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FIGURE 3
(a) Electron micrograph of a gold sol prepared by the citrate route. Reproduced from Ref. [19] with permission from The Royal Society of Chemistry. (b)–(e)
TEM images of gold nanoparticles with different shapes. Reprinted with permission from Refs. [20,21]. Copyright 2004/2010 American Chemical Society. (f )
TEM images of gold nanoparticles with increasing aspect ratios from a to e, corresponding absorption spectra and photograph of the dispersions. Reprinted
with permission from Ref. [22]. Copyright 2005 American Chemical Society. (g) High-resolution TEM image of CdSe nanocrystals. Reproduced from Ref. [23].
Copyright 2001 American Chemical Society.

of the corresponding dispersions change from pink to blue, green biomedicine makes them a primary focus in nanoparticle research
and brownish. [27]. In addition to organometallic routes [28], heat-up methods
Regarding the synthesis of semiconducting nanoparticles with a [29], and polyol-mediated syntheses [30], hydrolytic [31] and non-
defined size and size distribution, the introduction of the hot hydrolytic/nonaqueous [32] sol–gel approaches have been parti-
injection method represented a significant milestone. In 1993, cularly successful for the preparation of metal oxides. For nanos-
Murray, Norris and Bawendi reported a simple route for the cale materials, nonaqueous sol–gel methods seem to have some
production of high quality CdE (E = S, Se, Te) quantum dots in advantages over aqueous processes mainly with respect to the high
the range of 1.2–11.5 nm [24]. The synthesis involved the rapid crystallinity of the particles and the accessibility of a wider range of
injection of an organometallic precursor into a hot coordinating compositions of the products [33]. Nonaqueous sol–gel routes
solvent to produce instantaneous nucleation. Further growth of involve the reaction of various types of molecular precursors
the nuclei into nanocrystals proceeded at a lower temperature, so (metal halides, metal acetates, metal acetylacetonates, metal alk-
that new nucleation events were suppressed. The separation of oxides, among others) with an organic solvent or a mixture of
nucleation and growth is an important parameter to achieve a organic solvents with or without any surfactants, followed by
high degree of monodispersity (Fig. 3g) [25]. Nowadays the hot heating in the temperature range of typically 50–2508C [34].
injection method has been adapted to prepare many other nano- Depending on the synthesis temperature, the heating step is
crystalline semiconductors [26]. performed in an oil bath, in an autoclave or in a microwave reactor
Another important class of materials are metal oxides, which (Fig. 4, upper part). There are several advantages connected to
offer a unique variety of structures, compositions and properties. these nonaqueous sol–gel methods. Most importantly, the nano-
Their potential applications in emerging fields such as energy particles are highly crystalline and a broad range of sizes, shapes
storage and conversion, catalysis, photocatalysis, sensing and and compositions is accessible, covering all types of properties

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FIGURE 4
Upper part: schematic of the nonaqueous and surfactant-free liquid-phase synthesis approach to metal oxide nanoparticles using autoclave, oil bath or
microwave heating. Lower part: TEM images of selected metal oxide nanoparticles synthesized by the nonaqueous approach.

including magnetic, electronically conductive, or ferroelectric gold nanoparticles remains an unresolved issue [35]. However, the
materials (Fig. 4, lower part). reasons why the mechanistic aspects of nanoparticle formation are
not well understood is not due to a lack of effort within the
Formation mechanisms scientific community, but due to the high complexity of the
Although nanoparticle synthesis has made great progress in the reaction pathways. Experimental studies have to include all
last few years and reached a very high level of sophistication, our aspects of nanoparticle formation such as pre-nucleation processes
understanding of nanoparticle formation lags considerably [36–38], nucleation and growth [39,40], assembly and agglomera-
behind. As a matter of fact, systems that have been known for a tion [41], chemical reaction pathways [42] and the solid–liquid
long time, such as the preparation of gold nanoparticles by the interface [43]. As a matter of fact, the experimental observations
citrate route, are still not yet completely understood. It is amazing often contradict the classical models or the generally accepted
that more than 50 years after the publication of the work of understanding and therefore the theoretical concepts have to be
[(Figure_5)TD$IG]Turkevich et al. [19] the role of citrate in the formation of the continuously adapted to the new findings [44,45].

FIGURE 5
TEM and SEM images of ZnO nanostructures grown in benzyl alcohol after different reaction times (upper panels) and the corresponding schematic
illustration (lower panel).

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One material which has been synthesized in a tremendous Assembly

variety of nanostructures is ZnO [46]. The corresponding synthesis About 20–30 years ago, the major part of nanoparticle research was
routes are as manifold as the underlying chemical mechanisms clearly focused on the development of synthesis techniques.
[47], and the complex morphologies are a direct result of the Nowadays, synthesis work is still important, but additionally,
crystallization pathways. One such example is the growth of the use of nanoparticles as building blocks, like LEGO bricks,
ZnO nanorods that assemble into fan-like bundles (Fig. 5) [39]. and their assembly into larger structures represents a rapidly
The reaction between zinc acetylacetonate and benzyl alcohol growing branch of research [49]. Considering, how many nano-
results after 1 min in undefined agglomerates, which transform particles with different compositions and properties are available
into particles with a triangular, fir tree-like morphology after and how many possibilities one has to mix and arrange them, it is
3 min. With continuous reaction time, the shape changes into obvious that such a toolbox opens up fascinating options for the

RESEARCH: Review
fan-like structures consisting of angled nanorods (Fig. 5, upper preparation of new materials. However, the controlled assembly of
panels). The schematic illustration (Fig. 5, lower part) summarizes nanoparticles crucially depends on the ability to understand and
these experimental observations. After a first nucleation, the master interparticle interactions such as van der Waals, electro-
primary particles assemble into triangular nanostructures. Addi- static, magnetic, molecular and entropic forces [50]. Unfortu-
tional nucleation and growth of primary particles continuously nately, on the nanoscale it is very difficult to estimate the
provides the building blocks for further attachment to the nanos- relative contributions of the different interactions, because they
tructures, finally resulting in rod-like nanoparticle stacks. This all fall within the same order of magnitude and it is therefore not
particle-based growth occurs in a crystallographically controlled acceptable to neglect any parameters [49]. As a consequence, the
way along the c-axis. The bottlenecks between adjacent particles formation of most nanoparticle assemblies can be modeled and
are then filled up by surface reconstruction, finally resulting in justified only a posteriori and very few examples are known where
smooth nanorod surfaces. The unusual aspect of this crystalliza- the course of nanoscale self-assembly was predicted prior to the
tion mechanism is that several nucleation events occur and that experiment. Therefore we shall not discuss this topic here (the
the growth of the nanostructures involves nanoparticle assembly reader is referred to dedicated reviews [50,51]) and just present a
as well as classical growth by incorporation of the monomeric few examples on nanoparticle assembly.
species on the surface of the nanostructures. In spite of such an In spite of the fact that nanoparticle assembly is currently a hot
intricate growth behavior involving several processes occurring in topic, the first examples were published more than 20 years ago.
parallel, the final nanostructures are surprisingly uniform in size Bentzon et al. prepared 7 nm sized iron oxide nanoparticles by the
and shape. thermal decomposition of Fe(CO)5 in decalin with oleic acid – one
Such complex crystallization mechanisms are of course not at of the standard procedures still used nowadays for iron oxide
all restricted to ZnO, but have been reported for other oxides, for nanoparticles [52]. Due to the high monodispersity, the nanopar-
example tungsten oxide nanoplatelets [48] and molybdenum ticles formed micrometer-sized ‘supercrystals’ (today called super-
dioxide nanorods [37]. What is common in all these systems is lattices) stacking in an hcp or fcc structure, just like atoms in
that despite the apparent simplicity of the synthesis route, typi- crystals [53].
cally just involving a precursor and a solvent, the nanostructure A next step on the way to increase the complexity of nanopar-
generation followed a rather complicated pathway. The study of ticle assemblies is the usage of binary nanoparticle mixtures, i.e.,
crystallization mechanisms can be tedious and time-consuming, building blocks of different compositions and sizes [54]. Thereby
however it is indispensable on the way to develop concepts for the the stacking behavior basically follows the same rules as for ionic
size- and shape-controlled synthesis of nanoparticles. crystals, where the size ratio of the building blocks and the charge

[(Figure_6)TD$IG]

FIGURE 6
(a) A scheme of the low-pressure chamber used for growing ordered binary assemblies. (b) TEM micrograph of 13.4 nm Fe2O3 and 5.0 nm Au nanoparticle
superlattice, isostructural with NaCl represented by the (1 1 1) projection, (c) three-dimensional sketch of NaCl unit cell, depicting the (1 0 0) and (1 1 1)
planes, respectively, and the minimum number of layers in the (1 0 0) and (1 1 1) projections necessary for the formation of the patterns identical with the
observed ones. Reprinted with permission from Ref. [54]. Copyright 2006 American Chemical Society.

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of the ions are mainly responsible for the resulting structure. lattice, typically represented by (1 1 1) projections (Fig. 6b and c).
Fig. 6a shows schematically, how these assemblies are deposited These ordered domains extend over several microns, which is
on a substrate from colloidal solutions. A mixture of 13.4 nm impressive for such superlattices, but orders of magnitudes too
Fe2O3 and 5 nm Au nanocrystals of 5 nm pack into a NaCl-type small for a ‘real’ material. One way to increase the size of the

[(Figure_7)TD$IG]
RESEARCH: Review

FIGURE 7
(a) Schematic illustration showing the assembly of nanoparticle clusters into one-dimensional periodic structures using a magnetic field. The strength of the
magnetic field determines the distance between the clusters and thus the observed color. (b) Photographs of aqueous dispersions of Fe3O4 colloidal
nanocrystal clusters in response to an increasing magnetic field. Reprinted with permission from Ref. [56]. Copyright 2012 American Chemical Society. (c)
Photographs of the different steps to prepare a titania aerogel from the nanoparticle powder: powder – wet gel monolith – supercritical dryer – close-up of
the reactor chamber of the supercritical dryer with a gel inside. (d) Photograph of a gold–titania aerogel, (e) TEM image of a gold–titania aerogel, (f )
photograph of an iron oxide-titania aerogel attracted by a magnet.

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nanoparticle assemblies is the use of external forces. Bergstrom high-tech product. Therefore it might be surprising that large scale
et al. applied a magnetic field to assemble nanoparticles on a TEM applications of nanoparticles entered our daily lives decades ago,
grid [55]. At the initial stage of the drying process, the dispersion of and they are not particularly spectacular. A prominent example
the magnetic iron oxide nanocubes is shortly exposed to a mag- along these lines is carbon black. It is an amorphous powder,
netic field perpendicular to the substrate. This is sufficient to consisting of nanoparticles in the size range of typically 20–
induce the development of small, highly ordered and crystallo- 50 nm. Its annual industrial production amounts to an unbelie-
graphically aligned nanocube clusters. During the drying process, vable 10 million metric tons, worldwide [65]. Over 90% of carbon
the clusters grow in a self-assembly process to nanoparticle super- black is used for the reinforcement of rubber, mainly car tires. It is
lattices that extend over several micrometers in the lateral dimen- produced by the incomplete combustion of heavy aromatic oil or
sions and about 300 nm in height. natural gas.

RESEARCH: Review
One example, which elegantly combines the size-dependent A completely different application of nanoparticles is in food
properties of individual nanoparticles with the collective proper- products. Amorphous silica nanoparticles are used as anti-caking
ties of the assemblies are responsive superparamagnetic colloidal agent to maintain the flow properties in powder products (e.g.,
photonic crystals [56]. In the first step, superparamagnetic iron instant soups) and to thicken pastes [66]. The conventional form
oxide nanoparticles are arranged into relatively monodisperse of amorphous silica is known as food additive E551. Like in the
spherical clusters, which are dispersed in a liquid medium as case of many other nanopowders, it is controversially debated,
schematically shown in Fig. 7a. At this stage, the color of the whether E551 is a nanomaterial or not, because during the pro-
dispersion is typically brown. Applying a weak magnetic field duction process the nanosized primary particles agglomerate to
makes it possible to assemble these colloidal clusters into ordered larger structures [66]. From a characterization point of view, it is
particle arrays. The periodicity leads to strong optical diffraction, often very difficult to distinguish primary particles from aggregates
so that different structural colors (Fig. 7b) can be obtained depend- or agglomerates.
ing on the strength of the magnetic field (which determines the Another major application of nanoparticles is in cosmetics,
distance between the particles). The colors can be fixed in a curable especially in sunscreens. Sunscreens contain titanium dioxide
polymer matrix. The fascinating aspect in this case is that the and zinc oxide nanoparticles, because they are colorless and
nanoparticle clusters, despite their building blocks being just a few reflect/scatter ultraviolet light more efficiently than larger particles
nanometers in size, respond to an external stimulus in such a way [67]. The small size of nanoparticles provides the benefit of making
that an optical effect is produced that can be seen by naked eye. them transparent, which results in better consumer acceptance
The only way to produce a macroscopic body from nanoparti- and thus improves the protection of human skin against UV-
cles is to assemble them in three dimensions and over several induced damage.
lengths scales. One example, which is solely based on a self- Amazingly, taking advantage of optical effects to improve the
assembly process, is the preparation of titania aerogels from pre- appearance of materials is still a major application of nanoparti-
formed anatase nanoparticles. A powder of surface functionalized cles, just as in ancient times. A prominent example is automotive
titania nanoparticles (3–4 nm in diameter) is dispersed in water coatings, which consist of several layers [68]. The two topmost
and gelled at slightly elevated temperatures (Fig. 7c). The wet layers are the colored base coat and the clear coat which protects
monolith is subsequently dried in supercritical CO2, resulting in the paint from the environment. Mercedes-Benz brought nano-
a nanocrystalline titania aerogel consisting of nanoparticles that particle-based clearcoat into series production for both metallic
are arranged into a 3-dimensional network from the nano- to the and non-metallic paint finishes by the end of 2003. The coating
centimeter-scale [57]. These anatase aerogels show outstanding fulfills a practical and an esthetical role. On the one hand it
specific surface areas and high porosity. The preparation of nanos- increases the scratch resistance, and on the other hand it visibly
tructured bulk materials from preformed nanoparticles represents enhances the gloss (Fig. 8a).
a highly flexible modular approach to a large variety of new Liquid magnets, so-called ferrofluids, represents another exam-
materials, as different types of nanoparticle can be co-assembled ple of nanoparticles at work. Because ferrofluids are ultrastable
in this way. For example, a mixture of gold and titania nanopar- suspensions of small magnetic nanoparticles in a liquid, they
ticles leads to a photocatalytic material (Fig. 7d) active under combine the normal behavior of a liquid with superparamagnetic
visible light. TEM images show the fine nanoparticle network with properties. In the presence of a magnetic field, the magnetic
embedded gold nanoparticles (Fig. 7e). If magnetic nanoparticles moment of the nanoparticles try to align with the magnetic field
are incorporated in the aerogel, then a macroscopically magnetic direction leading to a macroscopic magnetization of the liquid
monolith can be produced (Fig. 7f). (Fig. 8b). The possibility to control the flow properties of a ferro-
Nanoparticle assembly is one of the most fascinating and most fluid as well as its position inside a technical device lead to a
rapidly developing sub-areas in nanoparticle research [58]. The countless number of applications in devices such as dynamic seals
targeted architectures range from mesoporous materials [59], to and dampers [69,70]. But music enthusiasts also appreciate ferro-
metal and semiconducting aerogels [60], responsive and dynamic fluids as heat transfer materials in loudspeakers.
nanoparticle assemblies [61,62], macroscopic-scale nanowire films In addition to these mass applications, selected nanoparticles
[63] and nanoscale helices [64]. have found their way into more sophisticated, high-tech products.
However, the timeline from the discovery in the laboratory to a
Applications commercial product is typically very long. For example, from the
If one thinks about possible applications of nanoparticles, then the first report on the use of titanium dioxide nanoparticles in a dye-
first thought is usually that it has to be sophisticated; some type of sensitized solar cell [71] it took more than 20 years to develop a

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FIGURE 8
Photographs of (a) a Mercedes car with a nanoparticle clearcoat. Copyright Daimler AG. (b) Ferrofluid (picture by Andrew Magill) and (c) solar keyboard
folios for iPads. Copyright Logitech.

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