Вы находитесь на странице: 1из 8

www.advmat.

de

By Ludovico Cademartiri, and Geoffrey A. Ozin*


This paper is dedicated to Geoff Ozin on the occasion of his 65th birthday

RESEARCH NEWS

Ultrathin NanowiresA Materials


Chemistry Perspective

This important characteristic potentially


allows the inorganic ultrathin nanowires
to outperform carbon nanotubes (CNTs) in
a variety of applications that involve solution
processibility, such as microfluidics[11] and
paint-on electronics; CNTs are known to be
scarcely dispersible in solvents. Colloidal
stability also allows the study of certain
properties of nanowire synthesis (like
absorption cross-sections) in a more comfortable way.[12,13]
Closely related with their potential
colloidal stability is the possibility of
designing the surface chemistry of the
nanowires by ligand exchange; while this is
also true for thicker nanowires, the ultrathin diameter amplifies the importance of
this possibility. Bioconjugation techniques
to employ nanowires for in vivo biodetection[14] or as regeneration scaffolds[15] can
now be imagined, together with the tuning
of their surface charge, to create layer-by-layer films of nanowires
with nanometer-controlled thickness.[16]
Nevertheless, what really inspires a large number of scientists
is the possibility of synthesizing, stabilizing, and isolating large
numbers of ultrathin nanowires with the unprecedented
structures predicted by theory.[17] Most of the work has been
performed on metallic nanowires, from elements such as Al,[17]
Pb,[17,18] Bi,[19] Si,[2022] Rh,[23] Ag,[24] Cu,[25,26] and Au.[27,28] In the
case of Al, Pb, Au, Cu, Rh, and Bi, wires below a certain size have
been found to preferentially adopt a multiwalled architecture.
The stability of the outer surface determines the stability and
properties of the entire structure; this explains the theoretical
findings that surface vacancies on such wires would migrate to
the core,[25] that melting would first occur in the core,[28] or that
the core might be entirely missing, leading to a tube
architecture.[29] The outer surface of the wires is predicted to
show, in certain ranges of diameter, a helical twist, which would
give an unprecedented chirality to the nanowires,[17] similarly to
CNTs. Preliminary experimental evidence for such helicity has
been obtained in Au nanowires[30] and Pt nanotubes.[29]
While there are a few reports of single ultrathin metallic wires
and tubes suspended between electrodes in ultrahigh vacuum
conditions,[29,30] there is the necessity to access such structures in
a much less demanding way. It is possible that solution-phase
syntheses will soon allow obtention of that size regime, where
new structures emerge. One concern is that the ligand strategies

The recent years have seen an explosive interest in one-dimensional


nanostructures,[1] as testified by the number of citations this field has accrued; as
customary, its blossoming was enabled by chemical breakthroughs that allowed
the reproducible and affordable synthesis of such structures.[2,3] The limitations
of those syntheses was in the diameter of the nanowires that it could produce
(hardly < 10 nm), and in the use of expensive and low-yield techniques, such as
chemical vapor deposition (CVD).
This paper attempts to summarize the very recent chemical breakthroughs
that have allowed the production of ultrathin nanowires, often in solution,
and often in gram-scale quantities. By no means is this a comprehensive
coverage of the field, which can in part be found in other excellent
reviews,[1,2,46] but a selection of those contributions that we feel would most
help put this emerging field in perspective. We will review the various
synthetic strategies, their pros and cons, and we will give our best guesses as
to the future directions of the field and what we can expect from it.

1. Introduction: Why Ultrathin Nanowires?


The term ultrathin is unscientific, as it does not explicitly specify a
size range. Ultrathin nanowires are considered to be less than
10 nm in diameters in most of the literature; we will see, though,
that an especially large interest is emerging in nanowires below
23 nm. The attractive characteristics of ultrathin nanowires are
summarized in Figure 1. One aspect correlated with decreased
diameter is the increased surface area, which in turn, has
immediate repercussions on sensors,[7] catalyst supports,[8] and
environmental-remediation applications.[9,10]
Less obviously, the decrease in size of the nanowires leads to a
certain degree, to an increased colloidal stability: the gravitational
force is easier to counteract by applying colloidal-stabilization
strategies involving coulombic repulsion or steric stabilization.
[*] Prof. G. A. Ozin, Dr. L. Cademartiri [+]
Materials Chemistry Research Group
Department of Chemistry
University of Toronto
80 St. George Street, Toronto
Ontario M5S 3H6 (Canada)
E-mail: gozin@chem.utoronto.ca
[+] Present address: Dept. of Chemistry and Chemical Biology, Harvard
University, 12 Oxford Street, Cambridge, MA 02138, USA.

DOI: 10.1002/adma.200801836

Adv. Mater. 2009, 21, 10131020

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1013

RESEARCH NEWS

www.advmat.de

Figure 1. Potential of ultrathin nanowires: the various areas of interest behind the research on ultrathin nanowires are shown, together with possible areas
of application.

that are generally used to maintain nanostructures colloidally


stable might alter the very reason why such weird structures
emerge: the delicate equilibrium between surface and core
energies.
The properties of such ultrathin nanowires are of great
interest, as they have been demonstrated to show quantum
conductance and ballistic conduction.[31] Negative magnetoresistance,[32] localization,[31] low thermal conductivity,[33] ferromagnetism,[34] and quantum size effects[35] are other properties that
are of great importance for a variety of applications. For example,
the low thermal conductivity of one-dimensional nanostructures
is expected to boost the efficiency of thermoelectric devices, as
recently demonstrated in silicon nanowires.[36,37]
The last point of interest for ultrathin nanowires we would like
to stress is the possibility of studying the fuzzy interface between
nanowires and molecular entities. Questions that arise are

whether we can observe polymer-like topological properties in


inorganic nanowires, if we can couple molecular properties, like
monodispersity, with the quantum size effects of nanoscale
materials, and what the interface between these two worlds would
look like.

2. Ultrathin-Nanowire Synthesis Methodologies


The synthetic methodologies that have been employed for the
synthesis of ultrathin nanowires are all within the nanowire-synthesis framework described by Xia et al.[1] More specifically
they mostly involve templating, ligand control, and oriented
attachment. In Figure 2, we have listed the tools, the pros, and the
cons of each of these strategies, which we will individually cover
through some case histories.

Figure 2. Ultrathin-nanowire synthesis methodologies: the tools and pros and cons of the different synthetic strategies to obtain ultrathin nanowires are
shown.

1014

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2009, 21, 10131020

www.advmat.de

Adv. Mater. 2009, 21, 10131020

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

RESEARCH NEWS

how silicon, germanium, copper, cobalt, and iron oxide


nanowires could be created within pores by supercritical
inclusion techniques, which take advantage of the extremely
The templating strategy involves the use of a hard or soft
low viscosity and surface energy of supercritical fluids.[4043] An
structure, called the template, as the directing agent of the growth
example of the magnetite nanowires produced by this technique
of the nanowires. The isotropicity of crystal growth is constrained
is shown in Figure 3c. Ko and Ryoo showed, instead, how wet
by the asymmetry of the template. As shown in Figure 2, the
impregnation with metal-salt solution allowed the formation of
templates can be zeolites, mesoporous materials, nanocrystals, or
metallic nanowires within the pores of mesoporous materials,
micelles.
which could also be extracted from the template.[44] This
Romanov showed that molten bismuth could be infiltrated in
technique has then been used to produce a variety of nanowires
the natural zeolite Mordenite to obtain ultrathin nanowires only
of different metals.[45,46] The reduction of the salts was performed
two atoms across.[38] Hong et al. used an organic analog to a
by UV irradiation. Ultrathin polymer nanowires have been
zeolite instead, obtained by the self-assembly of calix-4-hydroproduced by in situ polymerization of phenolformaldehyde
quinones.[39] The redox activity of the calixarene was used to
within the pores of PMS.[47] As shown in Figure 3d, those fibers
reduce silver ions in situ, and the result was the formation of
had
a strong tendency to aggregate in bundles, a very common
silver nanowires 0.4 nm thick embedded in the matrix (Fig. 3a
feature
of nanowires liberated from mesoporous materials, as
and b). In these cases, the wires were not extracted from the
they lack specific surface stabilization.
template.
Templating can also be performed by nanocrystals through the
In the case of mesoporous materials, like periodic mesoporous
vaporliquidsolid (VLS) reaction protocol, in which a molten
silicas (PMS), the pores are between 2 and 30 nm in diameter,
metallic nanocrystal templates the dissolution and precipitation
permitting an easier infiltration. Holmes and coworkers showed
of the precursors, and gives the onedimensional symmetry.[5] In Figure 3e, a
5 nm Si nanowire growing along the (110)
axis with the templating Au nanocrystal at its
tip is shown.[48] A similar mechanism was used
by Korgel and coworkers to form Si and GaAs
nanowires in supercritical solvents (Fig. 3f and
g).[49] In this case, the nanowires were not stuck
to a surface, as in the case of VLS methods, but
were instead dispersed in the fluid phase. By
using Bi/Au alloy colloidal nanocrystals, Kunos
group demonstrated the synthesis of veryhigh-quality ultrathin CdSe[50] and CdTe[51]
nanowires in solution at relatively low temperatures.
Recently, a flurry of papers has appeared in
the literature regarding Au ultrathin nanowires. In the first report, Xias group reported
the reduction of gold chloride salts through
oleylamine and silver nanocrystals.[52] The
mechanism they propose is the formation of
an [(oleylamine)AuCl]n inorganic polymer,
which templates the formation of ultrathin
nanowires with uniform thickness. The polymer is shown in Figure 3h, and the product in
Figure 3i. Preliminary evidence of such
polymer chains was demonstrated.
A few days after, Suns and Liebers group
reported the electrical characterization of
Figure 3. Templating strategies: a) HRTEM image of Ag nanowire arrays, formed in a self-assembled
samples obtained in very similar conditions.[53]
calix [4] hydroquinone matrix. [39] b) Proposed atomic structure for the Ag nanowires in a). [39] c)
HRTEM image of Fe3O4 nanowires produced in a mesoporous silica material by supercritical Au single-crystal nanowires of 9 nm diameter
inclusion. [42] d) TEM image of poly(phenolformaldehyde) ultrathin nanowire bundles formed after were found to have a good conductivity and a
removal of the PMS template. [47] e) Ultrathin Si nanowires grown by VLS methodthe scale bar is high failure current density. This work demon5 nm. [48] f,g) TEM and HRTEM images of ultrathin Si nanowires grown in supercritical solvents by strates that ultrathin nanowires can circumvent
nanocrystal templating. [49] h) Drawing of an [(oleylamine)AuCl]n inorganic polymer, which tem- the electromigration problems of nanowires,
plates the gold nanowires depicted in i). l) HRTEM image of gold nanowires grown via a micellar
which leads to failure. These wires are thus
mechanism. [54] Reproduced with permission from [4]. Reproduced with permission from [39,49].
Copyright 2001, 2000 American Association for the Advancement of Science. Reproduced with expected to be very promising for nanoelecpermission from [42,48,54]. Copyright 2003, 2004, 2008 American Chemical Society. Reproduced tronic circuitry. In a report which followed by
few days, Yangs group obtained a similar
with permission from [47]. Copyright 1998 Royal Society of Chemistry.
2.1. Templating

1015

RESEARCH NEWS

www.advmat.de

product (shown in Fig. 3l) via a similar procedure involving gold


chloride salts and oleylamine.[54] In that work, the formation of
the wires is attributed to a micellar mechanism.
The micellar growth mechanism is based on the assumption
that the micelles formed by the long-chain alkylamines would
guide the growth of the nanowires in one dimension. The
curvature of the micelle at the tip of the nanowires would lead to a
very loose packing of the alkyl chains, which in turn would allow
for easier diffusion of the reagents to the tips.[55] At the same
time, the alkylamines can slowly reduce the metal salts. Some
doubts remain on this proposed mechanism, based on the fact
that oleylamine (sometimes with oleic acid impurity) is generally
used as the ligand in these reactions. Oleylamine has a double
bond in the middle of the chain, which usually prevents the
formation of ordered monolayers stabilized by van der Waals
interactions. The micelles produced by oleylamine were thus not
expected to be strong, well ordered, and dense enough to
completely prevent the growth of the nanowires in two directions.
In Xia and coworkers interpretation of the Au-nanowire growth
mechanism,[52] the micelle is not really the template. According to
their results, the nanowires are formed by the reduction and
coalescence of [(oleylamine)AuCl] inorganic polymers. In this
case, the stability of the one-dimensional
architecture during growth would be granted
by the AuAu bonds along the backbone of the
polymer, instead of by an oleylamine micelle.
The micellar-templating mechanism was
also proposed for the formation of FePt
nanowires by Sun and coworkers,[55] for the
growth of calcium phosphate[56] and barium
sulfate[57] nanofibers by Mann and coworkers,
and for the growth of ultrathin Te nanowires
by Qian and co-workers.[58] The attractiveness
of the micelle- and polymer-templating
mechanisms is that they can marry the best
aspects of a templating strategy with the
advantages of ligand-control strategies, which
are routinely used for the synthesis of
monodisperse
spherical
nanocrystals.
Together with monodispersity and the large
know-how available, the possibility exists to
obtain large amounts of colloidally stable
material. In addition, one is not necessarily
limited by anisotropic structures, as often
happens for ligand-control strategies.

caps very strongly the sides of the nanostructure, thus strongly


reducing its surface energy and therefore its growth rate, while
the other ligand caps selectively and loosely the tips. This selective
ligand shielding, coupled with the high chemical potential of the
tips (due to their curvature and different lattice terminations),
allows for the formation of nanowires with high aspect ratios.[60]
In some cases, the presence of two ligands is not necessary, as the
difference in surface energy of the different facets of the
nanostructure are already high enough to favor one-dimensional
growth.
Some exceptionally thin nanowires have been obtained by this
methodology. Qian and coworkers demonstrated the growth of
Cu2S nanowires as thin as 1.7 nm (Fig. 4a).[61] A mixture of
decanethiol and oleic acid was used, and the morphology of the
wires was found to be strongly dependent on the precursor ratio.
Similarly, the morphology of Bi2S3[62] and Sb2S3[63] nanowires and
nanotubes was also dependent on the precursor ratio, as reported
by our group and by Son and coworkers.[64]
Bi2S3 nanowires were formed via a heterogenous nanocrystal
route,[65] by reacting a bismuth citrate slurry in oleylamine with a
sulfur solution in oleylamine[62] (Fig. 4b). The diameter was
found to be extremely monodisperse and independent of reaction

2.2. Ligand Control


Ligand-control strategies for the synthesis of
nanowires was an offspring of the work that
was being done on shape control of nanocrystals. The first demonstration of the controllable synthesis of CdSe nanorods demonstrated that using mixtures of ligands on
anisotropic structures (like CdSe wurtzite)
allowed for the growth of anisotropic structures.[59] The principle is simple: one ligand

1016

Figure 4. Ligand control strategies: a) HRTEM image of 2 nm Cu2S nanowires produced by


decomposition of single-source precursor Cu{S2CNEt2} in the presence of decanethiol and oleic
acid. [61] b) TEM image of 1.6 nm necklace Bi2S3 nanowires produced by the reaction of bismuth
citrate with sulfur in oleylamine. [62] c,d) TEM image of 1.1 nm  2.2 nm samaria nanoribbons
produced by high-temperature decomposition of samarium acetate in presence of oleylamine and
decanoic acid. [66] e) TEM and HRTEM images of 1.2 nm ceria nanowires produced by hightemperature decomposition of cerium nitrate in the presence of diphenyl ether, oleic acid, and
oleylamine. [67] Reproduced with permission from [61,66]. Copyright 2005, 2006 American
Chemical Society. Reproduced with permission from [62,67].

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2009, 21, 10131020

www.advmat.de

2.3. Oriented Attachment


Oriented attachment is maybe the most fascinating growth
strategy for ultrathin nanowires,[6870] where single-crystalline
nanowires are produced by oriented aggregation of faceted
nanocrystals.[4,71] This methodology has some unique features,
such as the constancy of the nanowire diameter during growth,
and the similarity with polymerization reactions, in which
monomers are added to the tip of the growing polymer.[72] The
attachment is usually driven by the formation of a permanent or
temporary electric (or magnetic) dipole in each nanocrystal. The
dipoles then orient in chains and attach. The matching of the

Adv. Mater. 2009, 21, 10131020

dipoles with specific facets of the structure allows for the final
nanowire to often maintain single-crystallinity. The advantage of
oriented attachment is that the diameter of the nanowire is largely
determined by the diameter of the nanocrystals. The ease with
which nanocrystals with small diameters (<4 nm) can be
prepared renders this technique promising in the production
of ultrathin nanowires.
Ultrathin CdSe nanowires were obtained by oriented attachment by reacting cadmium acetate (CdAc2) and selenourea in
long-chain amines.[73] The diameter of the final wires could be
tuned by changing the reaction temperature, or by using different
long-chain amines. Longer-chain amines produced larger wires
(Fig. 5a and b). In a following theoretical paper,[74] the same
authors found that the formation of low-aspect-ratio quantum
dots or rods followed by oriented attachment was the most
energetically viable route to nanowires, confirming the experimental data. In the wurtzite structure of CdSe, the c axis can show
facets entirely capped by cations or anions; this is a strong
premise to the formation of dipoles in the structure during
growth. ZnSe, another wurtzite solid, was also formed in the
shape of ultrathin nanowires by oriented attachment, by reacting
selenourea with cadmium acetate in the presence of molten
octadecylamine (Fig. 5c).[75]
In all the examples mentioned above, very strong quantum
confinement effects were observed, testifying to the crystallinity
and small diameter of the wires. While it is true that oriented
attachment is easier to obtain on structures possessing an
anisotropic lattice, such as wurtzite, recent experiments have
demonstrated that cubic structures can also undergo oriented
attachment in spectacular ways.
PbSe nanocrystals undergo oriented attachment to form
straight or zigzag nanowires, or even nanorings.[76] The shape of
the final assembly depends on the ligands that stabilize the
nanocrystal building blocks; octahedral nanocrystals were formed
by using alkylamines, which strongly coordinate the (111) facets,
which led to the formation of zigzag nanowires such as the ones
shown in Figure 5d and e. Straight nanowires could be obtained
using oleic acid instead, which preferential caps (100) facets.
Nanorings were obtained by oriented attachment along different
directions simultaneously. An important result of that work was
that it demonstrated via simple probabilistic considerations that
cubic structures could consistently show dipoles along various
crystallographic directions, by virtue of the polarity of the (111)
facets.
Recently, Patla et al. showed how the simple decomposition of
lead hexadecylxanthate in trioctylamine could lead to the oriented
attachment of PbS nanocrystals, to form PbS nanowires 2 nm
thick (Fig. 5f and g).[77] Those nanowires would spontaneously
assemble in parallel arrays, and undergo lateral-oriented
attachment if compressed laterally in a LangmuirBlodgett
trough. Nanowires 2 nm wide would coalesce to form 610 nm
nanowires. In2Se3, another cubic structure, could also be coerced
into ultrathin nanowires, by oriented attachment of rod-like
nanocrystals[78] using a heterogeneous synthesis strategy.[65]
A puzzling aspect of the oriented-attachment mechanism is
that it seems to occur also in metals that are not expected to form
long-lived dipoles on their surface, given their free-electron cloud
and cubic lattices. Despite these considerations, Au nanowires
were obtained by oriented attachment, by reacting chloroauric

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

RESEARCH NEWS

time. The structure of the wires was compared to a necklace, as it


was composed of nanocrystalline grains along the backbone of the
wire. Optical spectroscopy and photoconductivity experiments
demonstrated the presence of quantum confinement effects and
of excitons at room temperature, never before seen in Bi2S3. The
exact mechanism of growth is still largely unknown, but we
postulated, on the basis of our experiments, that some specifically
stable one-dimensional configuration of the atomic structure of
Bi2S3 must lie at about 1.6 nm,[62] much like what happens for
magic clusters. This is further confirmed by the ubiquitous
1.6 nm size in nanostructures formed from the isostructural
Sb2S3.[64,65] This strong valley in the energy landscape would
prevent the nanowire to grow sideways, and instead would foster
growth along one direction only. Sb2S3 nanowires and nanoplatelets could be formed with a thickness of 1.7 nm, by reacting
antimony oleate with sulfur dissolved in oleylamine.[63] Similarly,
nanotubes formed by the rolling up of a 1.7 nm-thick ribbon could
be formed by reacting SbCl3 with sulfur in oleylamine.[64] In this
case, different from Bi2S3, the nanowires were single crystalline.
Metal oxide nanowires were also produced in ultrathin
diameters by Hyeons group. Sm2O3 nanowires, shown in
Figure 4c and d, had a rectangular cross-section of 1  2 unit cells,
corresponding to 1.1 nm  2.2 nm.[66] The nanowires were grown
by decomposing hydrated samarium acetate in the presence of
oleylamine and decanoic acid at high temperatures. The
peculiarity of this reaction was its sensitivity to the specific fatty
acids. The same reaction performed with oleic acid gave ultrathin
platelets instead of wires.
By dissolving and decomposing cerium nitrate in diphenyl
ether, oleylamine, and oleic acid, ceria nanowires with a diameter
of 1.2 nm were obtained.[67] Wires with different lengths were
produced by using different amounts of oleic acid, but also in this
case the thickness was found to remain constant.
The ligand-controlled reactions have now demonstrated the
feasibility of producing ultrathin nanowires of a variety of
materials, irrespective of anisotropicity of the lattice. The last two
examples of samaria and ceria both have cubic structures. The use
of more than one ligand is also unnecessary, as the cases of Sb2S3
and Bi2S3 demonstrate. What is somehow clear is that a more
thorough understanding of the mechanisms of these reactions is
needed. Most of these examples show a remarkable selectivity for
some determined thicknesses, which is not consistent with
traditional ligand-controlled growth models. It is also possible
that some of these examples are unrecognized cases of
micelle-templated growth.

1017

RESEARCH NEWS

www.advmat.de

acid in oleylamine at reflux.[79] The reaction is almost identical to


the one later reported by Huo et al.[54] and Wang et al.,[53] who
gave a micellar-templating explanation for the results, as we
previously saw.

Pt and Pd nanowires of similar ultrathin diameter (4 nm)


were obtained by reducing Pd(NO3)2 or PtCl2 with NaBH4 in a
mixture of toluene, water, octadecylamine and n-dodecyltrimethylammonium bromide.[34]

3. Future Directions and


Challenges

Figure 5. Oriented attachment strategies: a,b) HRTEM image of CdSe nanowires synthesized by
reacting cadmium acetate with selenourea in the presence of long-chain amines of different
lengthsDDA stands for dodecylamine, while HDA stands for hexadecylamine. [73] c) HRTEM
image of ZnSe nanowires formed by reacting zinc acetate with selenourea in the presence of
octadecylamine. [75] d,e) HRTEM and TEM images of PbSe nanowires formed by reacting lead
oleate with trioctylphosphine selenide in the presence of oleic acid, and oleic acid and tetradecylphosphonic acid, respectively. [76] f,g) TEM and HRTEM images of PbS nanowires formed by
thermal decomposition of lead hexadecylxanthate in the presence of trioctylamine. [77] Reproduced
with permission from [73,76,77]. Copyright 2006, 2005, 2007 American Chemical Society. Reproduced
with permission from [75].

1018

The challenge in the synthesis of ultrathin


nanowires lies not so much in coercing the
structure to grow preferentially in one direction, but in completely halting the growth
along the other two directions. This is
accomplished by a barrier in the case of
templating, by reducing surface energy in the
case of ligand control, or by assembling
preformed building blocks, in the case of
oriented attachment.
The templating methodology has some
drawbacks, related to the template removal,
the colloidal stability, and the scale-up to gram
scale. The micellar strategy is a hybrid
approach between template and ligand control, since the micelle is formed by the same
molecules that are generally used as ligands.
Its advantages are potentially many, but its
mechanism is still not clear. It is not apparent,
for example, if the micelles are formed due to
the presence of some water traces, and if their
role is necessary during the growth (which
often happens at high temperatures), or if
they are just responsible for the creation of an
intermediate structure, which then reacts to
form the wires.
The ligand-control methodology has shown
some impressive examples of ultrathin nanowires, but a common trait in most of those
reactions is the inability to gradually tune the
diameter of the nanowire. The occurrence of
material-specific magic diameters still has
to be experimentally validated in those
samples, but it is consistent with most
theoretical investigations of ultrathin semiconductor and metallic nanowires. Such a
mechanism would also explain how ligands
could completely stop the growth along two
directions, which is generally not the case for
bulkier nanostructures. More research is
necessary to further develop our understanding on this issue.
The oriented-attachment strategy still
remains highly fascinating, especially since
their discovery in cubic and metallic structures, which were not initially thought to
display strong enough dipole moments. A
more systematic approach to a series of
materials would probably allow better understanding of the conditions under which

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2009, 21, 10131020

www.advmat.de

Acknowledgements
G. A. O. is Canada Research Chair in Materials Chemistry. The authors are
deeply indebted to NSERC and the University of Toronto for financial
support. They are also humbled by the scientific contribution of all the
coauthors in the Ozins group papers referenced in this work. Several
relevant articles have appeared in literature between the date of submission
and publication. We highlight in particular the synthesis of ultrathin SnO2
nanowires by Xun Wang and co-workers by attachment mechanism[80], the
synthesis of ultrathin organosilica nanowires by Axel Muller and colleagues
by polymer templating[81], and the synthesis of ultrathin colloidal gold
nanowires by Luis Liz-Marzan and coworkers[82].

Published online: December 18, 2008

[1] Y. N. Xia, P. D. Yang, Y. G. Sun, Y. Y. Wu, B. Mayers, B. Gates, Y. D. Yin, F.


Kim, Y. Q. Yan, Adv. Mater. 2003, 15, 353.
[2] J. T. Hu, T. W. Odom, C. M. Lieber, Acc. Chem. Res. 1999, 32, 435.
[3] A. M. Morales, C. M. Lieber, Science 1998, 279, 208.
[4] Z. Y. Tang, N. A. Kotov, Adv. Mater. 2005, 17, 951.
[5] M. Law, J. Goldberger, P. D. Yang, Annu. Rev. Mater. Res. 2004, 34, 83.
[6] C. N. R. Rao, F. L. Deepak, G. Gundiah, A. Govindaraj, Prog. Solid State
Chem. 2003, 31, 5.
[7] Y. Cui, Q. Q. Wei, H. K. Park, C. M. Lieber, Science 2001, 293, 1289.
[8] J. M. Nhut, L. Pesant, J. P. Tessonnier, G. Wine, J. Guille, C. Pham-Huu, M.
J. Ledoux, Appl. Catal. A 2003, 254, 345.
[9] C. T. Yavuz, J. T. Mayo, W. W. Yu, A. Prakash, J. C. Falkner, S. Yean, L. L.
Cong, H. J. Shipley, A. Kan, M. Tomson, D. Natelson, V. L. Colvin, Science
2006, 314, 964.

Adv. Mater. 2009, 21, 10131020

[10] J. Yuan, X. Liu, O. Akbulut, J. Hu, S. L. Suib, J. Kong, F. Stellacci, Nat.


Nanotechnol. 2008, 3, 332.
[11] G. M. Whitesides, Nature 2006, 442, 368.
[12] V. Protasenko, D. Bacinello, M. Kuno, J. Phys. Chem. B 2006, 110, 25322.
[13] L. Cademartiri, E. Montanari, G. Calestani, A. Migliori, A. Guagliardi, G. A.
Ozin, J. Am. Chem. Soc. 2006, 128, 10337.
[14] N. W. S. Kam, H. J. Dai, J. Am. Chem. Soc. 2005, 127, 6021.
[15] G. A. Silva, C. Czeisler, K. L. Niece, E. Beniash, D. A. Harrington, J. A.
Kessler, S. I. Stupp, Science 2004, 303, 1352.
[16] G. Decher, Science 1997, 277, 1232.
[17] O. Gulseren, F. Ercolessi, E. Tosatti, Phys. Rev. Lett. 1998, 80, 3775.
[18] B. K. Agrawal, V. Singh, R. Srivastava, S. Agrawal, Phys. Rev. B 2006, 74, 12.
[19] B. K. Agrawal, V. Singh, R. Srivastava, S. Agrawal, Nanotechnology 2006, 17,
2340.
[20] M. Menon, D. Srivastava, I. Ponomareva, L. A. Chernozatonskii, Phys. Rev.
B 2004, 70, 6.
[21] I. Ponomareva, M. Menon, D. Srivastava, A. N. Andriotis, Phys. Rev. Lett.
2005, 95, 4.
[22] J. X. Cao, X. G. Gong, J. X. Zhong, R. Q. Wu, Phys. Rev. Lett. 2006, 97, 4.
[23] B. L. Wang, G. H. Wang, Y. Ren, H. Q. Sun, X. S. Chen, J. J. Zhao, J. Phys. :
Condens. Matter 2003, 15, 2327.
[24] J. J. Zhao, C. L. Buia, J. Han, J. P. Lu, Nanotechnology 2003, 14, 501.
[25] J. W. Kang, J. J. Seo, K. R. Byun, H. J. Hwang, Phys. Rev. B 2002, 66, 8.
[26] J. W. Kang, J. J. Seo, H. J. Hwang, J. Phys. : Condens. Matter 2002, 14, 8997.
[27] S. P. Ju, J. S. Lin, W. J. Lee, Nanotechnology 2004, 15, 1221.
[28] J. L. Wang, X. S. Chen, G. H. Wang, B. L. Wang, W. Lu, J. J. Zhao, Phys. Rev. B
2002, 66, 5.
[29] Y. Oshima, H. Koizumi, K. Mouri, H. Hirayama, K. Takayanagi, Y. Kondo,
Phys. Rev. B 2002, 65, 4.
[30] Y. Kondo, K. Takayanagi, Science 2000, 289, 606.
[31] J. I. Pascual, J. Mendez, J. Gomezherrero, A. M. Baro, N. Garcia, U.
Landman, W. D. Luedtke, E. N. Bogachek, H. P. Cheng, Science 1995,
267, 1793.
[32] K. Y. Arutyunov, Phys. C 2008, 468, 272.
[33] M. S. Dresselhaus, G. Chen, M. Y. Tang, R. G. Yang, H. Lee, D. Z. Wang, Z.
F. Ren, J. P. Fleurial, P. Gogna, Adv. Mater. 2007, 19, 1043.
[34] X. W. Teng, W. Q. Han, W. Ku, M. Hucker, Angew. Chem. Int. Ed. 2008, 47,
2055.
[35] X. Y. Zhao, C. M. Wei, L. Yang, M. Y. Chou, Phys. Rev. Lett. 2004, 92, 4.
[36] A. I. Boukai, Y. Bunimovich, J. Tahir-Kheli, J. K. Yu, W. A. Goddard, J. R.
Heath, Nature 2008, 451, 168.
[37] A. I. Hochbaum, R. K. Chen, R. D. Delgado, W. J. Liang, E. C. Garnett, M.
Najarian, A. Majumdar, P. D. Yang, Nature 2008, 451, 163.
[38] S. Romanov, J. Phys. : Condens. Matter 1993, 5, 1081.
[39] B. H. Hong, S. C. Bae, C. W. Lee, S. Jeong, K. S. Kim, Science 2001, 294, 348.
[40] N. R. B. Coleman, M. A. Morris, T. R. Spalding, J. D. Holmes, J. Am. Chem.
Soc. 2001, 123, 187.
[41] N. R. B. Coleman, N. OSullivan, K. M. Ryan, T. A. Crowley, M. A. Morris, T.
R. Spalding, D. C. Steytler, J. D. Holmes, J. Am. Chem. Soc. 2001, 123, 7010.
[42] T. A. Crowley, K. J. Ziegler, D. M. Lyons, D. Erts, H. Olin, M. A. Morris, J. D.
Holmes, Chem. Mater. 2003, 15, 3518.
[43] K. J. Ziegler, B. Polyakov, J. S. Kulkarni, T. A. Crowley, K. M. Ryan, M. A.
Morris, D. Erts, J. D. Holmes, J. Mater. Chem. 2004, 14, 585.
[44] C. H. Ko, R. Ryoo, Chem. Commun. 1996, 2467.
[45] Z. Liu, Y. Sakamoto, T. Ohsuna, K. Hiraga, O. Terasaki, C. H. Ko, H. J. Shin,
R. Ryoo, Angew. Chem. Int. Ed. 2000, 39, 3107.
[46] A. Fukuoka, Y. Sakamoto, S. Guan, S. Inagaki, N. Sugimoto, Y. Fukushima,
K. Hirahara, S. Iijima, M. Ichikawa, J. Am. Chem. Soc. 2001, 123, 3373.
[47] S. A. Johnson, D. Khushalani, N. Coombs, T. E. Mallouk, G. A. Ozin, J.
Mater. Chem. 1998, 8, 13.
[48] Y. Wu, Y. Cui, L. Huynh, C. J. Barrelet, D. C. Bell, C. M. Lieber, Nano Lett.
2004, 4, 433.
[49] J. D. Holmes, K. P. Johnston, R. C. Doty, B. A. Korgel, Science 2000, 287,
1471.

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

RESEARCH NEWS

dipoles are formed, and how those dipoles affect the growth of the
nanostructures. Monitoring the change of seed-particle concentration versus time of reaction would be highly important to
understand the specific kinetics of attachment, similarly to what
is done for polymerization reactions.
The challenges facing this field are impressive. Ultrathin
nanowires are very difficult to characterize by high-resolution
transmission electron microscopy (HRTEM), as they tend to melt
under the beam. In some cases, this has rendered the imaging
almost impossible,[62] even with a cooled stage. X-ray diffraction
methods are also very difficult to interpret, due to the extreme
difference of coherence lengths along different crystallographic
axes, leading to the overlap of extremely broad and sharp
features.[63,66] In addition, the peaks are expected to show some
measurable shifts with respect to the bulk structures, as the
nanowires experience a strongly anisotropic pressure due to their
surface curvature.
Also, given the fragility of these ultrathin nanowires,
single-wire measurements are challenging, especially in those
cases where the wires show a pronounced flexibility, which
renders them unlikely to align across electrodes.
Despite these challenges, we find this field to be at the verge of
a new blossom, as recent publications seem to suggest. The
chemistry aspects are more and more well-defined, and more
scientists can enter the fray by synthesizing their nanowires in
solution by simple and scalable techniques. More chemistry
awaits, stay wired!

1019

RESEARCH NEWS

www.advmat.de

1020

[50] J. W. Grebinski, K. L. Hull, J. Zhang, T. H. Kosel, M. Kuno, Chem. Mater.


2004, 16, 5260.
[51] M. Kuno, O. Ahmad, V. Protasenko, D. Bacinello, T. H. Kosel, Chem. Mater.
2006, 18, 5722.
[52] X. Lu, M. S. Yavuz, H.-Y. Tuan, B. A. Korgel, Y. Xia, J. Am. Chem. Soc. 2008,
130, 8900.
[53] C. Wang, Y. Hu, C. M. Lieber, S. Sun, J. Am. Chem. Soc. 2008, 130, 8902.
[54] Z. Huo, C.-K. Tsung, W. Huang, X. Zhang, P. Yang, Nano Lett. 2008, 8,
2041.
[55] C. Wang, Y. L. Hou, J. M. Kim, S. H. Sun, Angew. Chem. Int. Ed. 2007, 46,
6333.
[56] S. Sadasivan, D. Khushalani, S. Mann, Chem. Mater. 2005, 17, 2765.
[57] J. D. Hopwood, S. Mann, Chem. Mater. 1997, 9, 1819.
[58] G. C. Xi, Y. K. Liu, X. Q. Wang, X. Y. Liu, Y. Y. Peng, Y. T. Qian, Cryst. Growth
Des. 2006, 6, 2567.
[59] X. G. Peng, L. Manna, W. D. Yang, J. Wickham, E. Scher, A. Kadavanich, A.
P. Alivisatos, Nature 2000, 404, 59.
[60] X. Peng, Adv. Mater. 2003, 15, 459.
[61] Z. P. Liu, D. Xu, J. B. Liang, J. M. Shen, S. Y. Zhang, Y. T. Qian, J. Phys. Chem.
B 2005, 109, 10699.
[62] L. Cademartiri, R. Malakooti, P. G. OBrien, A. Migliori, S. Petrov, N. P.
Kherani, G. A. Ozin, Angew. Chem. Int. Ed. 2008, 47, 3814.
[63] R. Malakooti, L. Cademartiri, A. Migliori, G. A. Ozin, J. Mater. Chem. 2008,
18, 66.
[64] K. H. Park, J. Choi, H. J. Kim, J. B. Lee, S. U. Son, Chem. Mater. 2007, 19,
3861.

[65] L. Cademartiri, J. Bertolotti, R. Sapienza, D. S. Wiersma, V. Kitaev, G. A.


Ozin, J. Phys. Chem. B 2006, 110, 671.
[66] T. Yu, J. Joo, Y. I. Park, T. Hyeon, J. Am. Chem. Soc. 2006, 128, 1786.
[67] T. Y. Yu, J. Joo, Y. I. Park, T. Hyeon, Angew. Chem. Int. Ed. 2005, 44, 7411.
[68] J. F. Banfield, S. A. Welch, H. Z. Zhang, T. T. Ebert, R. L. Penn, Science 2000,
289, 751.
[69] R. L. Penn, J. F. Banfield, Science 1998, 281, 969.
[70] H. Colfen, M. Antonietti, Angew. Chem. Int. Ed. 2005, 44, 5576.
[71] Z. Tang, N. A. Kotov, M. Giersig, Science 2002, 297, 237.
[72] R. L. Penn, J. Phys. Chem. B 2004, 108, 12707.
[73] N. Pradhan, H. F. Xu, X. G. Peng, Nano Lett. 2006, 6, 720.
[74] A. S. Barnard, H. F. Xu, X. C. Li, N. Pradhan, X. G. Peng, Nanotechnology
2006, 17, 5707.
[75] A. B. Panda, S. Acharya, A. Efrima, Adv. Mater. 2005, 17, 2471.
[76] K.-S. Cho, D. V. Talapin, W. Gaschler, C. B. Murray, J. Am. Chem. Soc. 2005,
127, 7140.
[77] I. Patla, S. Acharya, L. Zeiri, J. Israelachvili, S. Efrima, Y. Golan, Nano Lett.
2007, 7, 1459.
[78] K. H. Park, K. Jang, S. Kim, H. J. Kim, S. U. Son, J. Am. Chem. Soc. 2006, 128,
14780.
[79] A. Halder, N. Ravishankar, Adv. Mater. 2007, 19, 1854.
[80] X. X. Xu, J. Zhuang, X. Wang, J. Am. Chem. Soc. 2008, 130, 12527.
[81] J. J. Yuan, Y. Y. Xu, A. Walther, S. Bolisetty, M. Schumacher, H. Schmalz,
M. Ballauff, A. H. E. Muller, Nat. Mater. 2008, 7, 718.
[82] N. Pazos-Perez, D. Baranov, S. Irsen, M. Hilgendorff, L. A. Liz-Marzan,
M. Giersig, Langmuir 2008, 24, 9855.

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2009, 21, 10131020