Current Opinion in Solid State and Materials Science 10 (2006) 182–191

Catalytic growth of nanowires: Vapor–liquid–solid,

vapor–solid–solid, solution–liquid–solid and solid–liquid–solid growth
Kurt W. Kolasinski
Department of Chemistry, West Chester University, West Chester, PA 19383, United States

Received 12 March 2007; accepted 12 March 2007

Abstract

Catalytic growth is a powerful tool to form a variety of wire (whisker) like structures with diameters ranging from just a few nano-
metres to the millimetre range. A range of phases (gas, solid, liquid, solution and supercritical fluid) have been used for the feeder phase,
i.e. the source of material to be incorporated into the nanowire. Solid, liquid, eutectic, alloy and metastable phases have all been invoked
to explain the structure of the catalytic particle. Rather than focussing on the differences that lead to the proliferation of an alphabet soup
of names for the various growth techniques, this review attempts to focus on the similarities between all of these catalytic growth pro-
cesses in an attempt to help stimulate a more universal understanding of the phenomenon. The review begins with a précis of the mate-
rials from which nanowires have been formed and then proceeds to a discussion of mechanistic aspects.
Ó 2007 Elsevier Ltd. All rights reserved.

1. Introduction tors have also been grown in 1D structures, primarily

As a controlled means of growing whiskers and more
recently nanowires, catalytic growth of solid structures
traces back to the discovery of Wagner and Ellis [1] that
Si whiskers could be grown by heating a Si substrate in a
mixture of SiCl4 and H2 with their diameters determined
by the size of Au particles that had been placed on the sur-
face prior to growth. Of course, the catalytic growth of car-
bon fibres has long been a recognized problem in the field
of catalysis [2]. In this case, such growth must be avoided,
for instance, in the steam reforming of CH4 over Ni cata-
lysts, which is the primary industrial source of H2.
The poster child of one-dimensional (1D) nanostruc-
tures is the carbon nanotube (CNT) either in single-walled
(SW-CNT) or multiwalled variants (MW-CNT). They are
valued for a wide range of extreme properties for electronic
applications, for their high thermal conductivity and for
their high strength [2–5]. A number of other semiconduc-
E-mail address: kkolasinski@wcupa.edu
nanowires, and are prized for their potential in electronic,
optoelectronic and sensing applications [*6–*8]. For more
on the potential of these nanostructures in applications,
the reader is referred to these recent reviews. Buhro and
co-workers [*9] have reviewed the formation of semicon-
ductor nanowires from solutions and supercritical fluids.
Here I concentrate on the production of 1D nanostructures
with the use of vapor phase transport and surface diffusion.
In the literature we might variously encounter nanowires
(solid core structures with diameters below 100 nm),
nanotubes (single or multi-walled hollow core structures
with diameters below 100 nm) and whiskers (larger solid
core structures). For simplicity, I will use the term nano-
wire generically to describe the structures formed by cata-
lytic growth unless I specifically want to call attention to
nanotubes or whiskers. This review does not attempt to
be exhaustive. Rather it looks first at a number of materials
systems that have been grown catalytically in the form of
nanowires, nanotubes or whiskers in the past year or
two. Then a review of the mechanistic aspects of catalytic
nanowire growth is made.

1359-0286/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cossms.2007.03.002
 K.W. Kolasinski / Current Opinion in Solid State and Materials Science 10 (2006) 182–191
2. Materials systems
Silicon was the system first investigated by Wagner and
Ellis [1] and it remains one of the most intensively studied
systems [7,10–14,*15,16–19]. Lieber’s group [*8] has stud-
ied silicon extensively including the formation of branched
Si nanowires (SiNW) [20]. Carbon nanotubes [2,21,22] and
carbon nanofibers [23] are also produced by catalytic
growth [24,25]. Heterojunctions between SiNW and CNT
have been formed [26]. Other materials that exhibit cata-
lytic growth of nanowires include SiOx (a substoichiomet-
ric silicon oxide) [27]; SiO2 [28,29]; Si1xGex [10,30]; Ge
[31,*32]; AlN [33]; c-Al2O3 [34]; oxide-coated B [*35];
CNx [36]; CdO [37]; CdS [38]; CdSe [*9]; CdTe [*9]; a-
Fe2O3 (hematite), e-Fe2O3 and Fe3O4 (magnetite) [39];
GaAs [15,40,*41,42,*43,44]; GaN [18]; Ga2O3 [18,45];
GaP [40,*41,*46]; InAs [*41,*47]; InN (hexangular struc-
tures) [48]; InP [*9,*41,42]; In2O3 [45]; In2Se3 [49]; LiF
[50]; SnO2 [45,51,*52]; ZnO nanowires [*7,*8,53] and nano-
plates [53]; ZnS [54]; ZnSe [55]; Mn doped Zn2SO4 [56]; and
ZnTe [57]. Let us now look at the conditions under which
catalytic growth has been used to create nanostructures so
that we can better understand the range of growth condi-
tions that have been used, as well as the similarities and dif-
ferences in growth characteristics that have been observed
so that we may generalize about some of the important
mechanistic characteristics.
An exciting development in the growth of single-walled
carbon nanotubes (SW-CNT) was reported by Takagi et al.
[*58]. A range of metal catalysts have been shown previ-
ously to work for the synthesis of carbon fibres and CNTs
[2]. Takagi et al. have shown that pyrolysis of ethanol can
be used in the presence not only of Fe, Co or Ni (the most
common catalysts) or Pt and Pd (which had been previ-
ously reported) but also the coinage metals (Cu, Ag and
Au). For the latter three metals to work not only do they
have to be clean to start with, they must also be smaller
than 5 nm in diameter for growth to be efficient. Their
explanation is that the metal particles are in a cluster-like
structure rather than a crystalline state, and C atoms are
soluble in these clusters. Then, C atoms might precipitate
to cover the surface of the nanoparticles, resulting in the
formation of a hemispherical cap with a graphitic structure
as the precursor of SW-CNT growth. They propose that
the essential role of metal particles is to provide a platform
on which carbon atoms can form a hemispherical cap from
which SW-CNT grow in a self-assembled fashion.
Si1xGex nanowires can be grown with a Au catalyst
much as SiNW can be grown as shown by Lew et al.
[30]. Growth was carried out in an isothermal quartz tube
reactor at 325–525 °C with a total reactor pressure of
13 Torr composed of a 10% mixture of SiH4 in H2 and
either a 1% or 2% mixture of GeH4 in H2 as source gases.
Higher temperatures (>375 °C) favour the growth of Si rich
(x < 0.5) Si1xGex nanowires; however, Ge thin film depo-
sition on the outer surface of the wire was observed at
increased GeH4/(SiH4 + GeH4) inlet gas ratios setting an
183
upper limit on the Ge fraction that can be obtained in this
temperature range.
Silanes do not have to be used as the source material for
the growth of SiNW and Si1xGex nanowires. Dujardin
et al. [10] have used a molecular beam epitaxy (MBE)
source and a substrate coated with a thin film of Au for this
purpose. The use of an MBE source is quite significant
because of a basic difference in the dynamics of the interac-
tion of an atomic vapor of Si as compared to SiH4.
Whereas the sticking coefficient of SiH4 is low on a Si
and practically zero on a H-terminated Si surface, it is
much higher on the surface of a metal catalyst. In contrast,
the sticking coefficient of Si atoms is unity on a clean or H-
terminated Si surface as well as on a metal catalyst particle.
Sun et al. [31] have created Ge nanowires (GeNW) by
evaporation of Ge powder in flowing Ar at 600 °C. Au
nanoparticles act as catalysts and are supplied from a col-
loidal solution of thiol-capped Au. The nanowires have
uniform diameters of 30 nm, are up to tens of microme-
tres in length and have a Au particle on their tip. The ori-
ginal size of the colloidal Au particles was 2 nm; hence,
significant aggregation must have occurred. Here we have
vapor phase transport of atomic Ge to already formed
Au catalytic particles.
Chandrasekaran et al. [*32] use a solid–liquid–solid
method to produce GeNW. Many lm long GeNW are
observed to emanate from the same mm diameter Ga cat-
alyst particle (multiprong root growth, as defined in the
next section). In and Sn are also suitable catalysts. A thin
film of the molten metal is spread on a Ge(1 0 0) wafer,
which is then exposed to a microwave plasma struck in
H2/N2. Ground NaCl is placed around the substrate. This
acts as a source of Cl, which in combination with the
plasma acts to transport the Ge. Alternatively, a quartz
substrate can be coated with the metal, and a powdered
mixture of NaCl and Ge is placed around the substrate.
Excitation involving a plasma is again used to elicit trans-
port and engender GeNW growth.
A Si wafer rather than a powdered sample has been used
as the source material for simultaneous growth of SiOx
nanowires and SnO2 nanobelts by Zhang et al. [27]. SnCl2
powder was placed upstream from a Si wafer and heated in
Ar + O2 to 950 °C for 2 h. The Sn catalyst particles, which
also contain several percent Si and O, form at the base of
the SiOx nanowires rather than the tips. Both the SiOx
nanowires and the SnO2 nanobelts experience multiprong
root growth.
Zhang et al. [38] also used catalysis over Sn nanoparti-
cles to form branched CdS nanowires. They mixed CdS,
SnO2 and graphite powders (in a 1:1:1 ratio) and heated
them to 1200 °C for 2 h under a constant flow of Ar. In this
case the Sn particle at the end of the nanowire is signifi-
cantly larger than the diameter of the wire that grows from
it. In both of the systems investigated by Zhang et al.,
vapor phase transport is used not only to supply the
growth material, but also to supply the material that forms
the catalytic particle.
184 K.W. Kolasinski / Current Opinion in Solid State and Materials Science 10 (2006) 182–191
Carbothermal reduction, vapor phase transport of
growth material and reaction with trace amounts of oxygen
have been utilized by Kuo and Huang in the growth of
CdO nanowires that are 40–80 nm in diameter and 30–
50 lm in length. CdO and graphite powders are mixed in
a 4:1 ratio. The silicon substrate is coated with a 1 nm
Au film and then placed 25 cm downstream from the reac-
tant mixture. The reactants are held at 500 °C and the
substrate at 400 °C. The Au particle at the end of the
nanowire has a diameter slightly smaller than the nano-
wire. Most of the nanowires have a smooth surface but
in an area of the reactor where there was probably a greater
amount of oxygen available, a jagged necklace structure
formed by a lateral growth of the rhombohedral CdO
nanocrystals over the smooth nanowires.
Pulsed laser deposition has been used by Morber et al.
[39] to synthesize FexOy and Mg doped e-Fe2O3 nanorods,
nanowires and nanobelts. The ablation target was a pressed
powder of magnetite (Fe3O4), which was placed next to a
quartz boat containing polycrystalline alumina wafer sub-
strates coated with a 2 nm Au film. Au particles are found
at the ends of the nanowires, therefore it appears that the
Au film spontaneously breaks up to form the catalytic
nanoparticles.
An arc discharge has been used by Li et al. [34] to form
cubic c-Al2O3 nanorods. The source material is a pressed
powder mixture of Fe and Al, surprisingly in a 60:40 ratio.
Fe catalyst particles are found at the ends of the nanorods.
The discharge is run in a mixture of 0.018 MPa Ar (99.9%
purity) and 0.008 MPa H2 (99.99% purity). The growth
conditions are highly non-equilibrium with the O being
supplied at the trace level as an impurity in the process
gases. The diameters of the c-Al2O3 nanorods are relatively
uniform, ranging from 20 to 30 nm.
Carbothermal reduction of a mixture of an Al3+ com-
plex with Fe powder has been used by Jung and Joo [33]
to create AlN whiskers. The mixture of the Al complex,
Fe and graphite was calcined at 1200–1500 °C for 5 h in
flowing N2. The whiskers often show modulations in their
diameters along the lengths of the whisker and the shapes
obtained depend on the growth temperature. This system
exhibits rather complex chemistry on account of the carbo-
thermal reduction to produce Al, dissociative adsorption of
N2, presumably on the Fe particles, and the formation of
Fe/Al/N alloy particles of the appropriate size.
Dendritic ZnO nanowires can be grown from Sn catalyst
particles as shown by Gao et al. [59]. They heated ZnO and
SnO2 powders (1:1 ratio) for 1 h under a pressure of 300–
400 Torr of Ar carrier gas. The nanostructures grew on
the top of the inner alumina wall of the tube furnace in a
region located downstream 15 cm away from the source
material, which was located in the middle of the furnace
at 1300 °C, and the local growth temperature was in the
range of 700–800 °C. The Sn particle is significantly larger
than the NW diameter. Note that in this system, as in sev-
eral others, there is a high proportion of the catalyst start-
ing material compared to the growth material. This stands
in contrast to, for instance, Au catalyzed growth of Si and
SiGe nanowires. Also in this system, both the growth and
catalyst phases are transported via the vapor phase. Taper-
ing to larger diameters is observed in this system, most
likely because the Sn nanoparticles are growing during
growth.
Xu et al. [53] formed ZnO nanowires with a hexagonal
cross section. Interestingly no catalytic particle is found
at the tip. Rather the catalytic action is provided by a
ZnBiIx thin film (a combination of tetragonal ZnI2 and
hexagonal BiI3). Mixtures of either BiI3 and Zn powder
or Bi and Zn powders were heated in flowing Ar to 250–
300 °C. The presence of I changes the growth direction of
the nanowires. The O can be supplied by an impurity in
the Ar but no growth is observed in the absence of Bi when
only Zn or ZnI2 powders are used.
Carbothermal reduction can be used to produce ZnO
nanowires on a silicon substrate. Moreover, what Yang
et al. have shown is that growth can be switch away from
ZnO nanowires to Mn doped ZnSiO4 if MnCl2 Æ 4H2O is
added to the reaction mixture. The furnace system was
flushed with high-purity Ar gas to eliminate O2 and heated
to 1100 °C under a constant flow of Ar gas. Then, the
quartz boat was placed in the centre of the furnace and
held at 1100 °C under the same Ar flow. After reaction
for 50–60 min at 800–900 °C, the Si wafers, which are situ-
ated downstream of the reaction mixture, were coated with
a layer of nanowires. The majority of this material is com-
posed of a willemite phase (a-Zn2SiO4 with rhombohedral
structure) forming well-aligned nanorods with lengths of 2–
4 lm and diameters of 70–150 nm. The Zn catalyst is con-
sumed so there is a severe taper at the end of the wires and
no metal particle is found.
Simultaneous growth of ZnO and LiF nanowires has
been reported by Jiang et al. [50]. Zn acts as the cata-
lyst when LiF + ZnO powders are heated in Ar to
750–850 °C. The downstream deposition region has a
temperature in the range of 400–500 °C. Cubic-structured
single-crystalline LiF nanowires grew along the h0 0 1i
and h1 1 0i crystallographic directions with diameters of
100–500 nm and lengths of tens of microns. The authors
propose that there must be a barrier to the incorporation
of LiF into the lattice and the Zn particle acts to lower this
barrier and cause growth to be preferential at its base.
Very similar conditions can be used to grow In2O3,
Ga2O3 and SnO2 nanowires. Indeed, In2O3 and SnO2
nanowires can be grown simultaneously without cross con-
tamination or doping as demonstrated by Johnson et al.
[45]. Fifty nanometer Au particles were deposited from
solution onto the Si substrate placed downstream from
high-purity (6 N) metal reactant species (In, Ga, or Sn)
placed separately in a quartz boat. The furnace was heated
to 800–1000 °C under flowing N2. No oxygen was supplied
directly to the system other than as an impurity in the N2
or that which desorbs from the surfaces inside the furnace.
Rectangular In2O3 rods are capped with a rectangular Au
particle that is slightly smaller than the rod, whereas
 K.W. Kolasinski / Current Opinion in Solid State and Materials Science 10 (2006) 182–191
Ga2O3 nanowires appear to have a nearly spherical particle
at their tip.
Mohammad [60] has grown a variety of Ga and In con-
taining nanowires including GaN, InAs, InN, InGaAs,
InGaN, InGaAsN using self-catalyzed growth involving
either liquid Ga or liquid In droplets. Depending on the
conditions either multipronged root growth or single-
pronged float growth (defined in the next section) are
observed. A combination of carrier gas (N2 or H2) and
NH3, if required, flows over the metallic reagents placed
in BN boats. One of the reactant metals may also be placed
on the substrate. The distance between boats and the sub-
strate, the flow rates and the temperatures of the boats and
the substrate are all important variables that affect the
composition and characteristics of the nanowires. Autocat-
alytic growth shares much in common with and may actu-
ally be the mechanism behind what is called vapor–solid
(VS) growth, in which no catalyst is intentionally added
to the system. Nonetheless, if one of the components is a
low melting point metal such as Ga, In or Zn, a liquid cat-
alyst particle may result during growth even if now none is
intentionally added.
Yun et al. [*35] have heated a mixture of B + 40 wt%
B2O3 (which is a liquid at the growth temperature) in vac-
uum over a 5–20 nm film of Au on Si to 600–950 °C for
30 min. B nanowires coated with an oxide layer are formed.
Interestingly, a root growth mechanism, in which several
nanowires emanate from a single catalytic particle, occurs
at low temperature and float growth, in which one catalyst
particle sits atop each nanowire, occurs at high tempera-
ture. The catalyst particle is a Au–B eutectic and dissolu-
tion of not only B into the Au particles but also the
interaction of the eutectic with liquid B2O3 may be impor-
tant in describing the growth dynamics of bundles of nano-
tubes and the switching between root growth and float
growth.
Laser ablation has been used by Jia et al. [55] to produce
ZnSe nanowires. Contrary to previous experiments involv-
ing nanowire growth during laser ablation [61–63], the
wafer target was not placed in a furnace. The evidence
for self-catalytic VLS growth, as suggested by the authors,
is not conclusive.
ZnTe nanowires with an average diameter of 30 nm
and lengths >1 lm can be grown under the influence of a
Au catalyst. Janik et al. [57] used a MBE source and a 3–
20 Å film of Au coated onto a GaAs substrate. The nano-
wires, which are inclined about 55° to the (1 0 0) substrate
normal, have a zincblende crystal structure and their
growth axis is h1 1 1i. The growth temperature is at slightly
above 350 °C.
In2Se3 nanowires have been grown either with an Au
catalyst or with In acting as a self-catalyst by Sun et al.
[49]. In2Se3 powder was held at 900–950 °C and placed
upstream in flowing Ar from a Au or In coated silicon
wafer held at 650–700 °C. The nanowires are 40–80 nm in
diameter and up to 100 lm in length. The spherical Au par-
ticle found at the tip of the nanowire contains less than 5%
185
In, no detectable Se and is slightly larger than the nano-
wire. When a 30 nm In film is used for catalysis, no In par-
ticle is found at the end of grown nanowires. At the growth
temperature either Au or In would be liquids.
Chen et al. [36] have grown C5N nanotubes from pyri-
dine over a Fe–Co catalyst deposited on c-Al2O3. A mix-
ture of N2 and pyridine passes over the catalyst while
heated to 550–950°C. In this case, the catalyst particles
have an unusual conical shape. Not only do the appear
to poke into the growing nanotube, they also are attached
to the substrate rather than floating to the top of the nano-
tube even though only one tube grows from one particle. A
tapered particle that pokes into the core of a CNT has also
been noted by Hofmann et al. [22] during plasma enhanced
growth from C2H2 or CH4.
3. Mechanisms
Let us first start out with some generalities. The singular
attribute that usually leads to the conclusion that VLS
growth has occurred is that a metal particle of roughly
the same diameter as the nanowire is found at the end of
the wire. This, of course, does not determine the phase
of the particle during growth and this controversial aspect
will be dealt with further below.
Nanowires produced by catalytic growth are often
found to have a uniform diameter. The wires are not
always round but might also exhibit other crystallographi-
cally defined shapes, such as hexagonal ZnO or rectangular
In2O3. Under some conditions, particularly for long
growth times, tapering of diameter to smaller (or less com-
monly larger) values is found. Often growth requires a bit
of an induction period before uniform nanowires begin to
grow. These considerations are represented schematically
in Fig. 1.
The initial period before uniform growth commences is
associated with any of a number of processes. In some
cases, the catalytic particles must be formed by vapor phase
and/or surface diffusion transport or else their surfaces
have to be cleansed of impurities (oxides or terminating thi-
ols). The particles may be deposited directly, for instance,
from the evaporation of a colloidal solution with a well-
defined size. Alternatively, a thin film of metal can be evap-
orated directly onto a substrate and if the metal does not
wet the substrate, it will ball up into islands either immedi-
ately as the result of Volmer–Weber growth [64] or else
subsequently when the system is annealed, the onset of Ost-
wald ripening [65] will lead to a distribution of island sizes.
The particles might also result from an evaporation and
growth process that occurs during the initial stage, such
as when carbothermal reduction is used to generate a vol-
atile metal that proceeds to condense elsewhere in the reac-
tor. Indeed, catalytic particles form readily under a variety
of conditions from any number of high vapor pressure, low
melting point metals. Instead of being the exception, it
rather seems to be the case that the onus is on an investiga-
186 K.W. Kolasinski / Current Opinion in Solid State and Materials Science 10 (2006) 182–191
Initiation Steady State Termination
deposition transport to dr/dt < 0
nucleation growth
saturation interface
passivation
dr/dt > 0 of sidewalls
dr/dt = 0
time
Fig. 1. General considerations on the different regimes that occur during
catalytic growth of nanowires and nanotubes.
tor to show that catalytic particle are not involved in the
growth process.
Once the catalytic particles are formed or deposited,
they may still need to be primed for the growth of nano-
wires. For instance, the pure metal catalytic particle might
not be that active for nanowire formation. Instead, an
admixture of the growth compound and the metal might
be required to form an (unstable or stable) alloy, a true
eutectic or some other solid/liquid solution. In this case,
saturation of the catalytic particle with the growth material
or the formation of the proper composition may lead to an
induction period before growth. Note that the incorpora-
tion of a significant amount of growth material into the
catalytic particle is expected to change the volume and,
therefore, the diameter of the particle from its initial value.
Hence Ostwald ripening and incorporation of growth
material can both conspire to change the size of the cata-
lytic particles.
The growth of nanowires with a uniform radius is asso-
ciated with a steady state growth in which material is trans-
ported to the particle/nanowire interface. If the nanowire
radius is related to the particle radius and the particle
radius is constant, a natural explanation for a uniform
nanowire diameter is that the particles have reached a
steady state and their diameter is not evolving in this
region. If the incorporation of material is directed solely
by the particle and incorporation directly into the sidewalls
is suppressed, a constant particle diameter leads to a con-
stant nanowire diameter. The particle might be able to
affect the size of the nanowire either by direct matching
of the size of the nanowire to the size of the particle or else
by some mechanism involving the curvature of the particle
in which strain and lattice matching play a role.
Finally, a tapering to smaller diameters and cessation of
growth will occur if either the particle enters a phase in
which it is consumed, if the growth material is no longer
supplied to the system, or if the temperature is reduced
below a critical value. The temperature will play a role in
numerous processes, e.g. dissociative adsorption, surface
diffusion, bulk diffusion through the particle, in determin-
ing the composition of the particle by affecting solubilities
and thermodynamic stability of certain phases as well as
diffusion of metal atoms away from the particle.
Fig. 2 illustrates several other aspects of growth that
must be considered. Will the nanowire be produced from
root growth in which the catalyst particle is found at the
base of the nanowire, Fig. 2a, or by float growth, in which
the particle is located at the tip of the nanowire? Will multi-
ple prong growth ensue, Fig. 2c, in which more than one
nanowire emanates from each particle or will single-prong
growth occur, Fig. 2d?
A rather widely reported misunderstanding [1,66,67] is
that VLS growth occurs because the sticking coefficient
on a liquid is unity and must be higher than the sticking
coefficient on the solid. This has also been mistakenly
repeated in other fields of structure formation involving
growth [68]. For growth of SiNWs from silanes, which
have a much higher dissociative sticking coefficient on
the particle than on the substrate or sidewalls, the reason
for the greater rate of dissociation is because of the cata-
lytic action of the metal in the particle not the fact that it
is liquid. There is no general evidence for the assertion
that the sticking coefficient must be larger on a liquid than
a metal. Second, the assertion does not even apply gener-
ally to VLS growth. The success of MBE in semiconduc-
tor processing relies largely on the fact that the sticking
coefficient of numerous evaporated semiconductor materi-
als is virtually unity on a solid substrate regardless of its
composition. VLS growth in a MBE configuration, in
which the growth material is supplied by evaporation
from a crucible unto the substrate, has been demonstrated
for nanowires composed of, e.g. Si, SiGe and III–V com-
pounds. A sticking coefficient difference alone cannot
account for the formation of nanowires. Other factors
must also be considered that allow the nanowire/catalytic
particle interface to act as a sink for the incorporation of
new material into the nanowire at a greater rate than the
growth of the sidewalls or the thickness of the substrate
in between particle sites. For instance, the catalytic parti-
cle can lower the barrier that is present for the incorpora-
tion of new material at the growth interface as compared
to the nucleation of an island on a sidewall or the
substrate.
Fig. 2a and b also illustrate several dynamical process
that can affect growth. Adsorption occurs from the fluid
(whether gaseous, liquid or supercritical) phase. Adsorp-
tion might be molecular or dissociative and may either
occur (vii) on the nanowire (viii) on the particle, (ix) on
the substrate. A natural way for the catalytic particle to
direct material to the growth interface is if the sticking
coefficient (probability of adsorption) is higher on the par-
ticle and vanishingly small elsewhere. Diffusion of adatoms
will occur (i) across the substrate (if the sticking probability
is not negligible), (ii) across the particle and (iii) along the
sidewalls. Diffusion across the substrate and along the side-
walls must be rapid and cannot lead to nucleation events.
Nucleation of the nanowire anywhere other than on the
particle must be suppressed so that growth only occurs at
the particle/nanowire interface and so that sidewalls do
not grow independently of the axial growth. There may
 K.W. Kolasinski / Current Opinion in Solid State and Materials Science 10 (2006) 182–191 187

Fig. 2. The processes that occur during catalytic growth. (a) In root growth, the particle stays at the bottom of the nanowire. (b) In float growth, the
particle remains at the top of the nanowire. (c) In multiple prong growth, more than one nanowire grows from one particle and the nanowires must
necessarily have a smaller radius than the particle. (d) In single-prong growth, one nanowire corresponds to one particle. One of the surest signs of this
mode is that the particle and nanowire have very similar radii.

be (vi) diffusion of material through the catalytic particle in
addition to (ii) diffusion along its surface. Substrate atoms
might also be mobile. They might (v) enter the particle
directly or else (iv) surface diffusion along the substrate
can deliver them to the surface of the particle. Not shown
in the diagram is that atoms from the catalytic particle
might also be mobile and diffuse along the sidewalls and
the substrate.
Four major distinctions in the growth process are illus-
trated in Fig. 2: root vs. float growth and multiprong vs.
single-prong growth. The particle may either end up at
the bottom (root growth) or top (float growth) of the nano-
wire. In multiprong growth, Fig. 2c, more than one nano-
wire grows from a single particle. In this case, the radius of
the nanowire rw must be less than the radius of the catalytic
particle rp. In single-prong growth there is a one-to-one
correspondence between particles and nanowires. A natu-
ral means to exercise control over the nanowire diameter
in single-prong growth would be if the nanowire radius
determines this value and rw  rp. Here is should be men-
tioned that in single-prong growth, rw  rp is usually
observed but that the catalyst particle sometimes is signif-
icantly larger and occasionally is somewhat smaller than
the nanowire radius. In multiprong growth rw is not deter-
mined directly by rp but must be related to other structural
factors such as the curvature of the growth interface and
lattice matching between the catalytic particle and the
nanowire.
Quite a bit of discussion has revolved around whether
the catalyst particle is liquid or solid. In other words,
whether the mechanism of growth is VLS or VSS. As an
example, there have been several reports on the growth
of III–V nanowires – such as GaAs, GaP, InAs and
InP – that have invoked either a solid [*41,42,44,69,70]
or liquid [*43,*47,71] catalyst particle. Similarly, during
the growth of carbon nanotubes or fibres both liquid [21]
and solid [23] catalyst particles have been reported. What
is clear from these reports is that there are circumstances
under which the catalyst can be liquid and others in which
it can be solid and the nanowires that result do not appear
to be materially affected. In other words, while it is impor-
tant for characterizing the growth mechanism, as far as the
dynamics of nanowire and nanotube formation are con-
cerned, it does not appear to matter whether the catalytic
particle is liquid or solid. Therefore, any mechanism that
relies upon a particular phase for the catalyst cannot be gen-
erally true.
Likewise, the phase from which the growth material is
taken is of little consequence. The growth material may
come from a gas that is unreactive on the substrate and
only reactive on the catalyst surface, such as in the case
of SiNW growth from silane. It may come from an atomic
vapor that has unit sticking probability on both the sub-
strate and the catalyst, as in MBE growth of SiNW or
III–V compounds. It may come from a plasma, a solution
or even supercritical fluids. Hence, any model that requires
a particular phase for the growth material cannot be gener-
ally valid. What is required is that the growth material is
mobile and can readily reach the growth interface with a
low probability of nucleating a crystallite (alternate growth
front) anywhere other than at the nanowire/catalyst
interface.
188 K.W. Kolasinski / Current Opinion in Solid State and Materials Science 10 (2006) 182–191
This leads us to contemplate what is the nature of the
catalysis. Originally, Wagner and Ellis figured that the
catalysis was of an ordinary variety. The metal particle cat-
alyzed the decomposition of the molecule that supplied the
growth material. But we see that this does not have to be
the case for catalytic nanowire growth to proceed. The acti-
vation energy of growth can be associated with activated
adsorption or with surface or bulk diffusion. However,
the essential role of the catalyst appears to be in lowering
the activation energy of nucleation at the axial growth inter-
face. There is a substantial barrier associated with the for-
mation of the critical nucleation cluster at a random
position on the substrate or nanowire according to classical
nucleation theory. If the catalyst can lower the nucleation
barrier at the particle/nanowire interface, then growth only
occurs there. Any of a number of processes may be the rate
determining step depending on the exact conditions, but
the most important role of the catalyst particle is to ensure
that material is preferentially incorporated at the growth
interface.
Virtually all of the theoretical work on catalytic growth
has treated the VLS mechanism explicitly. Therefore, there
is little information on why root growth and multiprong
growth occur under some circumstances. We do not know
why a system such as the growth of B nanowires studied by
Yun et al. [*35] changes from multipronged root growth at
low temperatures to single-pronged float growth at high
temperatures. Root growth is also observed by Chen
et al. [36] for C5N nanotubes grown from an Fe–Co cata-
lyst but in this case the growth is single-pronged. ZnO
can exhibit root growth as shown by Xu et al. [53] for a
Zn-B-I thin film catalyst though it is more conventionally
grown in a float growth mode with, for instance, a Sn cat-
alyst [59]. Zhang et al. [27] report that both SiOx nanowires
and SnO2 nanobelts form via multiprong root growth from
an Sn/Si/O alloy catalyst whereas Al, Ni, Cu, Pd, Ag and
Au can all be used for float growth of SnO2 nanowires as
shown by Nguyen, Ng and Meyyappan [*52].
Theoretical approaches to nanowire growth can be sep-
arated into at least three different categories: molecular
dynamics, thermodynamics and kinetics. Molecular
dynamics has been used, for instance, by Rosén and co-
workers [24,72,73] to examine the growth of CNTs. Kinet-
ics (mass-transport) based models have been considered by
Verheijen et al. [40], Dubrovskii et al. [*15], Tersoff and co-
workers [14,16], Persson et al. [44] and Johansson et al.
[*41,*46]. Thermodynamic approaches trace back to Blak-
ely and Jackson [74] as well as Givargizov [67] and more
recently have been treated by Kwon and Park [75], Wang
et al. [12], Chandrasekaran et al. [*32], Chen and Cao
[76], Mohammad [60], and Tan, Li and Gösele [66,77,*78].
The Gibbs–Thomson effect expresses how a curved
interface affects the chemical potential of a body. This
causes the vapor pressure and solubilities to become depen-
dent on the size of a catalyst particle. Thermodynamic
treatments are then able to show how the Gibbs–Thomson
effect leads to nanowire growth rates that depend not only
on the growth parameters (pressure and temperature) but
also the diameter of the catalyst particle. It is often found
that, the growth rate should decrease with decreasing dia-
meter [67,76]. However, this conclusion depends on the
growth conditions [*46] since the extent of supersaturation
within the catalyst depends on the temperature and gas-
phase composition. A transition from smaller diameters
having lower growth rates to smaller diameter having
higher growth rates can occur as temperature and gas-
phase composition are changed.
Gösele and co-workers [66,77,*78] have examined
whether there is a thermodynamically determined mini-
mum size and the parameters that affect not only the nano-
wire size but also the size of the catalytic particle. During
SiNW growth in the presence of a Au catalyst, the catalyst
minimum size is determined by the vapor pressures of Si
and the metal. The SiNW minimum size is determined by
the catalyst composition and its size. They arrive at the
conclusion that there is no thermodynamically determined
minimum size, rather, that the minimum size is determined
by kinetic limitations. In the case of SiNWs, Tan et al. [77]
predict that the catalyst should be larger than the nano-
wire, but this is clearly not universally true for all materials.
Chandrasekaran et al. [*32] have attacked the problem
of trying to explain the nucleation of uniformly sized nano-
wires in multipronged root growth. They specifically trea-
ted the case of GeNW growth from Ga particles and
developed an expression for the nanowire diameter
4V m r
dc ¼
RT lnðX Ge =X lGe Þ
where dc is the diameter of the resulting nanowire, Vm is the
molar volume, r is the interfacial energy, and X Ge =X lGe is
the ratio of solute concentration at the point of instability
to the corresponding equilibrium solubility at a given tem-
perature, T. The agreement with experiment is reasonable
and predicts that the nanowire diameter should depend
on the temperature and the metal used for catalysis.
An important conclusion of the molecular dynamics
studies of Ding et al. [24,72,73] is that a thermal gradient
is not required for the growth of single-walled carbon
nanotubes. Their study shows that a concentration gradi-
ent is more important than a thermal gradient for the
growth of SW-CNTs on small metal particles. Further-
more, SW-CNTs growth can occur in the presence of an
opposing thermal gradient, ie, the SW-CNTs grow from
the hot region of the catalyst particle.
Experimental studies of growth kinetics are not numer-
ous. Verheijen et al. [40] have studied the growth of GaP
and GaAs in heterostructured GaP–GaAs nanowires.
GaAsNWs exhibit diffusion-limited growth wherein the
rate is determined by the partial pressure of both reagents
(trimethyl gallium or AsH3) but has little dependence on
the temperature. In what might be called classical VLS
behaviour, they show that activated PH3 dissociation on
the Au catalyst following Langmuir–Hinshelwood kinetics
is the rate determining step for GaP growth. Sidewall
 K.W. Kolasinski / Current Opinion in Solid State and Materials Science 10 (2006) 182–191
growth and axial growth can exhibit different temperature
dependencies and an observed decrease in axial growth rate
for both GaP above 500 °C and GaAs above 440 °C is
related to increased sidewall growth. Sidewall growth is
also involved in producing tapered nanowires. The sub-
strate can play an active role in the growth kinetics. Here
the SiO2 substrate suppresses epitaxial growth, whereas
epitaxial growth is competitive with nanowire growth on
III–V substrates.
Extensive studies of growth kinetics and the develop-
ment of a mass-transport model have also been performed
in Lund [*41,44,*46,70]. Seifert and co-workers [*46] have
developed a model of a nanowire growing from a metal
particle which need not be liquid. They make the following
assumptions: (i) the metal particle is assumed to be hemi-
spherical, (ii) there is steady state adatom diffusion on the
substrate and nanowire sides toward the metal particle,
(iii) the processes within the metal particle (diffusion) as
well as at the metal-semiconductor interface (nucleation)
need not be considered in detail, and (iv) the interwire sep-
aration is fairly large. The authors note that assumption
(iii) limits the generality of the model because there are
cases in which these processes are rate determining. None-
theless, for the specific case of III/V nanowire growth,
experimental growth conditions can easily be set to validate
these assumptions.
Their model describes a mass-transport-limited system
in which deposition occurs on the substrate as well as
on the nanowire walls and the metal particle. Growth is
favoured at the metal/semiconductor interface, which acts
as a sink, and is kinetically hindered on the substrate and
nanowire walls. Transport via diffusion across the sub-
strate and up the walls plays a vital role. The microscopic
details of this model are sketchy and the explanation for
why incorporation does not occur on the substrate and
walls is vague, nonetheless its phenomenological descrip-
tion of length versus radius for various temperatures is
quite good.
Tersoff and co-workers have investigated the Au cata-
lyzed VLS growth of SiNWs [14,16]. They use disilane
(Si2H6) as the source gas at 108–105 Torr. A thin film
of Au (2–3 nm) is deposited on a Si(1 1 1) substrate, which
is then heated to 500–650 °C. No detectable dependence of
growth rate on the wire diameter is observed. They ascribe
this rather unexpected result to the irreversible character of
dissociative adsorption on the catalyst surface, which is the
rate determining step for these conditions. They have also
observed periodic sawtooth faceting of SiNW walls during
growth. Growth occurs at the (1 1 1) facet at the end of the
wire; however, the size and shape of this facet oscillates
periodically. They explain this based on the balance of
forces generated by the surface energies of the wire and
the droplet. They also predict that this will be observed
in any system in which the orientations parallel to the
growth direction are not stable.
Perhaps the most general scheme to explain nanowire
growth is that of Dubrovskii et al. [*15]. They incorporate
189
the rate of adsorption, the Gibbs–Thomson correction for
the finite curvature of the surface, diffusion-induced NW
growth, and the nucleation-mediated growth at the
liquid–solid interface with allowances for tapering of the
nanowires. This enables them to make very specific predic-
tions. For example, the tapering of GaAsNW grown by
MBE on the GaAs(1 1 1)B surface at T = 590 °C can be
explained by the reduction in the Ga flux to the catalyst
caused by the high rate of desorption of Ga atoms from
the sidewalls. Tapering due to the nucleation and growth
of islands on the GaAs(1 1 0) sidewalls is not thought to
be significant since the activation barrier for nucleation is
too high. They also are able to reproduce well growth rates
as a function of nanowire diameter so that they can fit data
regarding the dependence of nanowire diameter on nano-
wire length and the nanowire length (for a given diameter)
as a function of growth temperature.
4. Conclusion
Characterization studies of catalytic growth are demon-
strating an ever larger array of systems that exhibit the
growth of nanowires and nanotubes. Our understanding
of catalytic growth, regardless of whether it is labelled
VLS, VSS, SLS, SCLS or otherwise, is becoming increas-
ingly sophisticated. However, may questions still remain
unanswered particularly regarding the size and position
of the catalyst relative to the nanowire, in other words,
regarding aspects of float versus root growth and single-
prong versus multiprong growth and why the particle can
be sometimes larger and sometimes smaller than the nano-
wire. It is now clear that growth can occur by autocatalysis
as well as by catalysis due to a foreign metal/alloy particle.
The catalytic particle can be either liquid or solid but this
does not really change the dynamics of growth. The result-
ing nanowires can be unitary, binary, ternary or even qua-
ternary compounds and they have been produced either
pure or in doped forms. In some cases, more than one type
of nanowire can be grown simultaneously. Catalytic
growth represents a powerful method for producing 1D
nanostructures and there certainly are many more surprises
to be discovered in this area of research.
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