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Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

Contents lists available at ScienceDirect

Progress in Crystal Growth and


Characterization of Materials
journal homepage: www.elsevier.com/locate/pcrysgrow

Catalyzed chemical vapor deposition of one-dimensional


nanostructures and their applicationsq
M. Meyyappan
NASA Ames Research Center, Moffett Field, CA 94035, United States

a b s t r a c t

PACS: This article reviews progress in the growth of one-dimensional


61.46.Hk nanomaterials such as carbon nanotubes and inorganic nano-
61.82.Fk wires. Catalyzed chemical vapor deposition has been the
81.15.Gh
preferred method to grow these materials for various applica-
81.16.c
tions requiring controlled growth on patterned and unpatterned
82.65.Jv
68.70.þw substrates. Both thermal and plasma chemical vapor deposition
85.35.p techniques have been widely used in the case of carbon nano-
tubes. In addition to the discussion on growth, a review of
Keywords: applications for one-dimensional nanostructures and future
A1. Nanostructures
directions is provided.
A1. One-dimensional nanomaterials
A1. Low temperature plasma
Published by Elsevier Ltd.
A1. Catalyzed growth
A2. Vaporeliquidesolid technique
A3. Chemical vapor deposition

1. Introduction

For more than a decade now, there has been tremendous interest in the growth, character-
ization and applications of nanomaterials in various fields. This interest has been fueled by the

q The term ‘catalyzed CVD’ is used here with some reservation, in recognition of the widely held belief that gold or other
metals serve as a catalyst in the VLS growth of various inorganic nanowires. This is indeed incorrect as pointed out in Refs. [101]
and [4] (chapter 6.4). A catalyst by definition enhances the rate of a reaction or growth process while remaining intact in the
process. In contrast, the activation energy of silicon nanowire growth using gold seeds is w130 kJ/mol which is about the same
as for silicon thin film deposition, indicating that gold does not help to increase the reaction rate [101]. Similarly, the activation
energy for GaAs nanowire growth is in the range of 67e75 kJ/mol which compares with the 67 kJ/mol activation energy for the
GaAs thin film growth by MOCVD. The role of the molten metal ‘seed’ droplets is at best that of a ‘soft template’ collecting and
guiding the precipitation of material into cylindrical form.
E-mail address: m.meyyappan@nasa.gov

0960-8974/$ e see front matter Published by Elsevier Ltd.


doi:10.1016/j.pcrysgrow.2009.01.001
2 M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

U.S. National Nanotechnology Initiative introduced in 2000 and since then, similar initiatives
worldwide have generated substantial research activities in nanotechnology. Nanomaterials
exhibit a very high surface area-to-volume ratio compared to bulk materials. Interface effects and
quantum effects become dominant at the nanoscale. Various physical, chemical, mechanical,
electrical and other properties become size dependent and thus are different from the corre-
sponding bulk values. For example, a 5 nm gold particle melts at nearly 200  C lower than the
bulk melting point of 1064  C [1]. Gold as a bulk material is inert; however as a nanoparticle it is
found to be useful as a catalytic material. The field of nanotechnology is about taking advantage
of such novel properties which arise due to the nanoscale and creating functional devices,
systems, etc. This is to be contrasted with the straightforward miniaturization leading to nano-
scale devices such as the nanoscale silicon CMOS moving along the path predicted by Moore’s
law. The research activities in nanotechnology focus on preparation of various nanomaterials,
characterization, understanding the origin of differences in properties between nanoscale and
bulk scale, process development, modeling and simulation, and application development in
various fields.
Of these nanomaterials, carbon nanotubes (CNTs) have received extraordinary attention because
of their interesting electronic and mechanical properties [2]. Configurationally, a CNT is equivalent
to a rolled-up graphite sheet. A single layer of graphene sheet in a rolled-up form is equivalent to
a single-walled carbon nanotube (SWCNT). The diameter is as small as 0.7 nm and the length,
depending on growth time, can be hundreds of microns. The SWCNT can be metallic or semi-
conducting depending on its chiral vector (n, m); when (n  m)/3 is an integer, the nanotube is
metallic and if not, it is a semiconducting structure. The diameter of the nanotube is given by
a(n2 þ nm þ m2)0.5/p where a is the lattice constant of graphite. The bandgap of a semiconducting
nanotube is given by 2dccg/D where dcc is CeC bond length (0.142 nm), g is the nearest-neighbor
hopping parameter and D is the nanotube diameter given above. Young’s modulus of SWCNTs is
over 1 TPa and tensile strength is over 200 GPa. For comparison, the corresponding values for steel
are 208 GPa and 0.4 GPa respectively [3]. Carbon nanotubes can sustain a maximum strain of about
10% which is much higher than any other material. Such extraordinary mechanical properties are
due to CeC covalent bonding and seamless hexagonal network architecture. Carbon nanotubes can
support current densities of 109 A/cm2, and thermal conductivity values as high as 3000 W/mK have
been predicted [3]. It is possible to attach other functional molecular groups to the sidewall or ends
of the nanotubes, a procedure commonly known as functionalization or derivatization. Multiwalled
carbon nanotubes (MWCNTs) are equivalent to structures with multiple layers of graphite sheet
rolled up into a tube. Thus the separation between adjacent walls is very close to that of the
interlayer separation in graphite. The MWCNT diameters can be tens of nanometers depending on
the number of walls.
Another class of nanomaterials widely under investigation across the world is inorganic
nanowires (INWs) [4,5]. In the last three decades the materials community has successfully grown
semiconducting, dielectric, metallic and other materials from groups IV, IIIeV, and IIeVI in the
form of two-dimensional thin films using chemical vapor deposition (CVD), metal organic chemical
vapor deposition (MOCVD), molecular beam epitaxy (MBE), and atomic layer deposition (ALD).
Single monolayer control, periodic quantum wells, large area deposition, and numerous other
advances in epitaxial growth have led to successful applications of thin films in electronics,
photonics, microelectromechanical systems (MEMS) and many other fields. Recent efforts have
focused on growing inorganic materials in the form of one-dimensional nanowires [4,5]. When the
NW radius is below a critical value, radial quantum confinement is possible. For semiconducting
NWs, bandgap increases with a decrease in diameter [6]. Nanowires exhibit good surface quality
unlike etched structures. Interesting properties of inorganic nanowires and opportunities to do
a new class of integrated devices using one-dimensional materials have led to an active area of
research in recent years.
Both CNTs and INWs have been grown using a variety of techniques. For example, SWCNTs and
MWCNTs have been grown using arc discharges and laser ablation [7]. Solegel and other solution
based techniques have been successfully used for the synthesis of various nanowires [5]. The focus of
this review however is restricted to chemical vapor deposition as this approach is amenable to
M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21 3

controlled growth on substrates suitable for various applications. In addition, CVD is a well-known and
versatile technique already in use in diverse industrial applications.

2. Catalyzed chemical vapor deposition

In conventional chemical vapor deposition, the feedstock is dissociated into various radicals and
other reactive groups in the gas phase. The energy for this activity is supplied via heating as in thermal
CVD or through the creation of a glow discharge (low temperature plasma) with energetic electrons as
in plasma CVD. In either case, the reactive species diffuse to the growth substrate, adsorb onto the
surface and participate in surface chemical reactions which create epitaxial thin films. This is how thin
films of amorphous carbon, diamond, silicon, SiO2, Si3N4, aluminum and a range of other materials are
produced by CVD and PECVD. To produce nanowire or nanotube forms of these materials using the
same or similar feedstock, energy sources, and bulk phase (gas or plasma) reactions as in thin film
epitaxy, some form of guidance or template would be needed to mold a cylindrical structure. Physical
templates such as anodized alumina and zeolite have been used for molding the nanowires and
nanotubes [4]. A successful and popular alternative is known as vaporeliquidesolid (VLS) technique [8]
which is essentially a catalyzed CVD.
In the VLS approach, the catalyst material on the substrate, regardless of how it is obtained, is in the
form of small molten droplets under the growth conditions. The source vapors diffuse from the bulk to
the substrate, adsorb onto the catalyst material, dissociate/react as appropriate to generate the atomic
or molecular species of interest (C, Si, Ge, etc.). These species dissolve into the droplets and when
supersaturation is reached within the catalyst droplets, the material begins to precipitate as wires and
continues to elongate (see Fig. 1). This guided, axial growth produces cylindrical nanostructures and
there is no epitaxy involved, as we know in thin film growth. However, anomalies can lead to radial
epitaxy which piles up material on the sides of the axially-elongating structure from the catalyst
droplet, and the end result would be conical or tapered structures [9].
Wagner and Ellis [8] were the first to coin the terminology ‘vaporeliquidesolid mechanism’ in their
preparation of silicon whiskers by the hydrogen reduction of SiCl4 using gold seeds as catalyst. The
conclusions from their work included [8,10]: (i) silicon whiskers do not contain an axial screw dislo-
cation; (ii) a seed such as a gold particle is needed to promote whisker growth; and (iii) the seed
remains at the tip of the whisker (as shown in the schematic in Fig. 1). This study asserted that the
whisker growth from the vapor source did not occur by the Frank screw dislocation mechanism [11],
instead by the VLS mechanism. A decade later, experiments and morphological characterization by
Givargizov [12,13] also confirmed VLS mechanism to be responsible for whisker growth of silicon and
germanium from vapor sources.
It is clear from the above discussion that the catalyst drops play a critical role and the NT/NW
diameter, morphology, growth orientation and growth rate are dictated by the catalyst particle size,
thermodynamic and eutectic properties. The catalyst material can be applied to the substrate by
sputtering, thermal evaporation, laser deposition or by other physical techniques. Typically, thin films
of only a few nanometers are required and at suitable temperatures, this film is expected to break into
droplets to catalyze growth. Necessarily, the catalyst particles will have a distribution of diameters and
be located randomly across the substrate. Even if monodispersed colloids of the catalyst material are
used, particles can migrate laterally or agglomerate under the elevated growth temperatures, which
may then randomize the diameter distribution and the particle location. If tight diameter and position
control are desired, then some form of patterning is the only alternative. Since the catalyst droplet
serves as a ‘soft template’ to guide the growth, the diameter of the resulting nanostructure tightly
correlates to the diameter of the catalyst particle [14e17].

3. Carbon nanotubes

The feedstock for CNT growth is some form of hydrocarbon gas such as CH4, C2H4, C2H2, benzene,
etc. [2] mixed with H2 and possibly also diluted with an inert gas such as argon or nitrogen. The growth
temperature typically is lower than the pyrolysis temperature of the chosen hydrocarbon to avoid
production of amorphous carbon impurities. The growth relies on the catalytic activity according to
4 M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

Fig. 1. Schematic of VLS growth. Courtesy of H.T. Ng.

VLS mechanism and the common catalysts for CNT growth include transition metals such as nickel,
cobalt and iron. As discussed before, these metals can be sputtered onto the substrate as a 1e10 nm
thin film or applied by other physical techniques as well. The literature also has numerous reports
wherein solution based techniques have been used to create the transition metal catalyst particles, for
example, starting from a metal nitrate solution. Typically, these approaches have several steps
involving metal reduction, calcination, drying, etc. and take several hours [18]. Also, solution based
approaches are not amenable for substrate patterning and integration into established device fabri-
cation schemes.
Common research scale reactors for CNT growth involve a 1e200 quartz tube mounted inside a single
zone furnace with mass flow controllers to meter the feedstock gases. The operation is usually at
atmospheric pressure. A typical growth run would involve ramping up the temperature to the desired
level under an inert gas flow, followed by the admission of the feedstock for a specified growth period.
At the end of the growth period, the reactor is cooled down under an inert gas flow prior to the removal
of the substrate. Commercial reactors to grow CNTs are available currently and these cold wall reactors
can accommodate 4e600 wafers. Some of the features of these reactors include vacuum operation, load
lock arrangement, monitoring growth temperature, computer control, etc. At the time of this writing,
CNT growth on large wafers has not been reported much in the literature.
Fig. 2 shows scanning electron microscopy (SEM) and transmission electron microscopy (TEM)
images of SWCNTs grown on a silicon substrate using methane as feed gas at a temperature of 900  C. A
1 nm thin film of iron is sputtered as a catalyst on top of an underlayer of Al (10 nm). The underlayer
may increase the surface roughness and provide more active nucleation sites [19,20]. In some cases, the
underlayer also acts as a barrier to prevent catalyst diffusion into the substrate, for example, when Fe is
M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21 5

used as catalyst to grow CNTs on a substrate of highly-oriented pyrolytic graphite (HOPG). The use of
underlayer precludes the need for pretreatment of the catalyst surface [19]. Some of the common
pretreatment techniques include reacting the catalyst surface with ammonia gas in CVD and exposing
to ion bombardment in an inert gas plasma in PECVD, both of which are aimed at producing catalyst
particles. Characterization of the catalyst film by atomic force microscopy (AFM) and TEM indicates
(not shown here) nanoscale iron particles are with diameters as small as 2 nm [20]. The diameter of the
SWCNTs in Fig. 2 is in the range of 1.2e1.8 nm. The nanotubes tend to bunch together like ropes due to
van der Waals attraction forces. The CNT growth is influenced by numerous parameters including
temperature, choice of feedstock, addition of H2, dilution with inert gases such as argon or nitrogen,
choice of catalyst and how the catalyst is prepared and applied to the substrate.
Fig. 3 shows a tower of MWCNTs grown by CVD using ethylene as feedstock at 750  C. Here, the
thickness of the iron catalyst layer is 10 nm on top of a 20 nm Al underlayer. The MWCNTs growing out
of neighboring catalyst particles support each other due to van der Waals attraction resulting in
a crowded tower-like growth. Though the ensemble looks vertical, individual tubes inside tower are
wavy. Scraping the tower off the substrate reveals catalyst particles at the bottom tips of the nanotubes
indicating VLS growth. It is possible to grow individual, freestanding, vertical carbon nanostructures
instead of towers using PECVD. But such structures are often disordered; instead of all the walls being
parallel to each other as in an ideal MWCNT, the plasma-grown freestanding structures may feature
a bamboo-like inner core as shown in Fig. 4. These are commonly called carbon nanofibers (CNFs) in the
literature and their properties are somewhat inferior to those of MWCNTs [2,21]. For example, the CNFs
exhibit higher resistivity than the MWCNTs of comparable diameter since the electrons have to hop
across the bamboo barriers. Another difference is that these freestanding nanofibers invariably feature
the catalyst particle at the top of the fibers as seen in Fig. 4. This tip growth mode is different from the
base growth in Fig. 3.
PECVD reactors for CNF growth reported in the literature have included direct current (dc), radio
frequency (rf) capacitive and inductive, and microwave power sources although the dc plasma has
been the most common approach [21]. While the plasma processes use the same feedstock as in
thermal CVD, dilution is critical in the plasma process to avoid amorphous carbon production. This is
because the low temperature plasma efficiently dissociates the hydrocarbon through electron impact
reactions. The species delivered to the catalyst surface in thermal CVD is essentially heated hydro-
carbon feedstock with very little of anything else such as radicals since the growth temperature is

Fig. 2. SEM (left) and TEM (right) images of single-walled carbon nanotubes.
6 M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

Fig. 3. SEM image showing a multiwalled carbon nanotube tower (top) and a close view of the MWCNT tower (bottom) (images
courtesy of Alan Cassell).

below the pyrolysis temperature [22,23]. So, any dissociation in thermal CVD occurs only on the
catalyst surface. In contrast, the plasma phase delivers a variety of radicals such as CH3, CH2, CH, H,
higher hydrocarbons through recombination reactions, and ions to the catalyst surface [23e25]. These
differences lead to different growth characteristics and morphology between the two approaches.
Most common techniques to characterize the nanotubes for establishing quality and number of
walls in a MWCNT include TEM and Raman spectroscopy. The latter is also useful to identify the
chirality of the SWCNTs. Fig. 5 shows Raman spectra of MWCNTs and plasma-grown CNFs collected in
the backscattering configuration using a 633 nm HeeNe laser for excitation. The tangential G band
centered at 1590 cm1 and D band centered at 1350 cm1 are common features of multiwalled
nanotubes, and both samples exhibit these features. However, the CNFs show an additional shoulder
peak at 1612 cm1 that is possibly related to the E2 mode. In addition, atomic force microscopy (AFM),
M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21 7

Fig. 4. Carbon nanofibers grown using an inductively coupled plasma reactor. (Left) SEM image and (right) TEM image of a CNF
showing bamboo morphology and catalyst particle at the tip (image courtesy of Quoc Ngo).

scanning tunneling microscopy (STM), Fourier transform infrared spectroscopy and X-ray diffraction
are also used to characterize nanotubes [2].
As-grown CNTs may contain amorphous carbon and catalyst metal impurities which must be
selectively removed prior to application development. Several purification protocols are available and
a review of purification and material characterization can be found in Ref. [2]. Addition of functional
groups to the sidewall or ends is desirable to modify the CNT properties as needed in the preparation of
composites, chem-bio sensors, gas storage, battery, supercapacitor and other applications. For example,
fluorination of SWCNTs by exposing to F2 vapor at 500e600  C results in the loss of conductivity of the
nanotubes [26]. Fluorinated nanotubes can be used as insulators in all carbon-based electronics with
metallic and semiconducting nanotubes. Introduction of surface carboxyl groups can lead to a signifi-
cant increase in the capacitance due to the increased hydrophobicity of CNTs in an aqueous electrolyte
[27]. This is of particular interest in the development of the so-called electric double layer capacitors.
While conventional approaches for functionalization follow wet chemical treatment, a dry approach
using a glow discharge is faster, efficient and uses minimum amount of chemical resources [28,29].

Fig. 5. Raman spectra of multiwalled carbon nanotubes and carbon nanofibers (image courtesy of Bin Chen).
8 M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

Here, an appropriate source gas is used in a low temperature plasma to produce the necessary func-
tional groups, and functionalization of SWCNTs with H, F, NH and other groups have been shown to be
rapid and efficient [28e30].
The interesting electronic, mechanical and thermal properties of CNTs have prompted a broad array
of application development activities. Table 1 provides a summary of applications along with the
property creating interest in that direction. The ability to support high current densities, combined
with high electrical conductivity and mechanical strength, has made carbon nanotube a candidate for
replacing copper as the next generation interconnect in integrated circuits [31e33]. Local and global
wiring and interconnects in DRAM applications are all possibilities for carbon nanotubes and nano-
fibers. While the properties and theoretical predictions based on them are attractive, the imple-
mentation faces technical challenges such as in situ growth of nanotubes (horizontal or vertical) in
place and low temperature growth compatible with CMOS processing requirements. Since CNT/CNF
growth is promoted by catalytic activity and reasonable growth rates seem to require catalyst acti-
vation temperatures as high as 500  C, low temperature or room temperature growth for integration
into device processing scheme appears to be difficult. Though there have been reports on CNT growth
at temperatures less than 500  C, invariably the material quality has been poor enough to erase the
advantages of nanotubes over copper. Even if the temperature and quality related issues can be
overcome, selective in situ growth needs extensive process development research in the future.
Because of these barriers, an alternative approach has been to ‘pick and place’ nanotubes (from bulk-
grown material, after purification) at desirable locations. An electric field may be used during the
process to align the nanotube along the chosen direction [34]. Since the nanotubes are typically in
a solution, it is possible and often appropriate to use dielectrophoretic techniques to position the
nanotubes as interconnects. Unfortunately, the yield of these approaches to date has been rather low to
stimulate interest from industry.
The high thermal conductivity of CNTs is attractive in the search for a replacement for thermal
grease which is a thermal interface material in cooling of the computer chips [35]. Since thermal
conductivity is high only in the axial direction, only aligned nanotubes and nanofibers are of interest to
meet the heat dissipation loads. Mats of CNTs do not exhibit attractive enough thermal conductivity
values to be useful. Vertical PECVD-grown CNF structures have been intercalated with a metal such as
copper to create a CNFeCu composite that can maintain structural integrity at packaging pressures of
w60 psi [36]. Thermal resistance values of 0.1 cm2 K/W have been reported for these CNTeCu
composites which are attractive for chip cooling.
Another application in integrated circuit manufacturing involves the use of CNT probes in atomic
force microscopy (AFM) as a profilometer to obtain the shape and depth of vias and trenches. This
critical dimension (CD) metrology is an emerging need in semiconductor manufacturing since
conventional profilometers face difficulties in imaging narrow and deep features. A MWCNT probe
w10 nm in diameter and 1e2 mm long can be an effective AFM probe to meet the CD metrology needs
[37]. Fig. 6 shows profilometry results using such a probe to image a photolithographic pattern
generated by interferometric lithography. SWCNT probes, due to their small diameter, are excellent for

Table 1
Summary of applications for carbon nanotubes.

Desirable property Application


Semiconducting and metallic nanotubes Transistors
Electromechanical properties Switch, memory device
High electrical conductivity, current carrying capacity Interconnects
High thermal conductivity Chip cooling
Strength, flexibility, aspect ratio AFM probes
Electrical conductivity, density EMI shielding
Property change upon gas adsorption (conductivity, capacitance) Chemical sensor
Electrical conductivity, strength, aspect ratio Nanoelectrode
Electrical conductivity, ability to attach DNA/RNA/other bioprobes Biosensor
High strength Composites
Large surface area, pore volume Gas storage, lithium storage, catalyst support
M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21 9

imaging thin films of metallic, semiconducting, dielectric materials as well as biological samples. These
probes are capable of atomic scale resolution and in addition, do not wear out rapidly unlike the
conventional micromachined silicon or Si3N4 probes [38]. In order to reduce thermal vibrations,
a SWCNT probe cannot be longer than approximately 75e100 nm. If longer probes are needed, it is
possible to selectively sharpen the tip of a MWCNT to about 1e2 nm by applying an electric field. This
creates a sharper probe capable of the resolution normally possible only with a SWCNT while retaining
the stability of the MWCNT as a probe. Imaging biological materials in their native aqueous environ-
ment is also possible by modifying the normally hydrophobic surface of the nanotube to hydrophilic.
This can be achieved by applying a thin coating of ethylene diamine on the CNT probe [39].
Whereas the above possibilities attempt to serve immediate niche needs in silicon CMOS fabrica-
tion, entirely carbon nanotube based electronics has also been envisioned. The progress, however, has
been rather slow and the primary obstacle is the inability to selectively grow semiconducting vs.
metallic single-walled nanotubes. Beyond that, much work needs to be done in terms of process
development for large scale wafer based fabrication. In the meantime, basic devices and circuit
elements have been demonstrated with performance potential exceeding silicon [40e45]. Field
emission by CNTs is one of the most investigated topics in the literature since nanotubes possess an
ideal high aspect ratio, small tip radius of curvature and low work function [46]. The threshold field
required for a 10 mA/cm2 emission flux is one to two orders of magnitude lower than that for materials
considered in the past such as silicon, tungsten, molybdenum, graphite, and diamond. All forms of
nanotubes e SWCNTs, MWCNTs, CNFs, mats, towers, freestanding isolated structures e have been
shown to be capable of field emission. The field emission test setup consists of a simple diode or triode
(with a gate between the two electrodes) configuration in an evacuated glass chamber. The CNT
cathode and phosphor-coated anode are separated typically by a few hundred microns. The field
emission currentevoltage characteristics are described by the FowlereNordheim relation:
 
I ¼ aV 2 exp bf1:5 =bV

where I is the emitted current, V is the applied voltage, f is the work function of the material, and b is
the field enhancement factor [46]. The major driver for this investigation is the potential in large scale
flat panel displays and low power computer and consumer electronic displays.
Carbon nanotubes have also been investigated for sensing gases, vapors and biomarkers. The
surface area and pore volume of the nanotubes are very high; for example, SWCNTs have been shown
to have a surface area of 1580 m2/g [47]. This large area can lead to large adsorption rates for gases and
vapors. If the adsorbed species changes some measurable property of the CNTs, then measuring and

Fig. 6. Profile of a photoresist pattern obtained using a multiwalled carbon nanotube probe (image courtesy of Cattien Nguyen).
10 M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

monitoring that property forms the basis for chemical sensing. It has been shown that resistance,
capacitance and dielectric constant of SWCNTs change reproducibly upon exposure to some gases and
vapors [48e50]. Numerous sensor demonstrations have been reported for monitoring NO2, SO2, CH4,
H2, HCl, Cl2, acetone, benzene, toluene, nitrotoluene, formaldehyde, to name a few, with applications in
biomedical, security, mining, and several other fields [48e51]. The sensitivity ranges from parts per
million to parts per billion for those analytes. Chemical sensors that take advantage of the CNT
conductivity change upon gas/vapor adsorption typically assume a transistor-like configuration with
the nanotubes as the conducting channel [51]. Compared to the conventional channel material of tin
oxide, the nanotube sensors offer higher sensitivity and also work at room temperature. Simpler diode
configurations have also been proposed to reduce the sensor complexity and hence the cost [48]. The
nanotubes themselves are not selective to any particular gas or vapor and in some cases, selectivity
may be possible with doping, functionalization or coating on the nanotubes. In addition, nanotubes
may not be responsive at all to some gases and vapors, that is, CNT conductivity may not perceptibly
change upon adsorption of that species. Again, coating, doping or functionalization may be able to elicit
a change in conductivity upon adsorption. Once this is possible, a universal approach to selective
sensing is the electronic nose configuration wherein an array of sensors is used in conjunction with
a pattern recognition algorithm [52]. The individual sensors in the array may differ from each other in
physical as well as material features; the latter may include pristine vs. doped or coated nanotubes.
In the case of biosensing, the role of the nanotube is that of a nanoelectrode. Compared to a micro-
or macroelectrode, the size difference between a nanoelectrode and a biological species such as DNA or
RNA is small enough to reduce the background noise. A probe molecule chosen specifically for the
target of interest is attached to the nanotube end. Mats or dense nanotube arrays are difficult to work
with for developing nanoelectrodes. Instead, PECVD-grown vertical carbon nanofibers are ideal in this
regard [53] since a nanoelectrode array can be readily prepared by filling the gap between the elec-
trodes with a dielectric (such as SiO2) followed by chemical mechanical polishing to yield a smooth top
surface of SiO2 with protruding nanofiber ends (see Fig. 7). DNA or RNA probes can be attached to these
fiber ends [53]. The distance between adjacent electrodes must be larger than the radial diffusion layer
of each electrode; otherwise overlap of these layers may result in a large micro- or macroelectrode
behavior instead of true nanoelectrode characteristics. For a 50e75 nm diameter nanofiber, the

Fig. 7. A nanoelectrode array consisting of carbon nanofibers surrounded by SiO2.


M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21 11

separation distance between two adjacent CNF electrodes is about 1.0e1.5 mm. Therefore, patterning of
the catalyst on the substrate is required to obtain the desirable nanofiber electrode diameter and
location. When probeetarget hybridization takes place, an electrical signal via impedance measure-
ment or electrochemical signal using an intermediate such as Ru(bPy)3 can be measured [53]. This
approach has the potential to exceed the sensitivity levels of common fluorescence based biosensing
with an advantage of the amenability for integration with microfluidics on the same chip to deliver the
fluid sample to the sensor. Applications for CNT-based biosensors include lab-on-a-chip, environ-
mental monitoring, pathogen detection, cancer and infectious disease diagnosis, water quality moni-
toring, etc. [54,55].

4. Inorganic nanowires

4.1. Semiconducting nanowires

There is an extensive literature on the growth of silicon and germanium nanowires using the VLS
technique [4,15e17,56e63]. As in silicon thin film epitaxy, silane/H2 or SiCl4/H2 feedstock can be used
although the latter requires higher temperatures for the generation of source radicals. The growth
temperature itself is determined by the choice of catalyst. Gold is the most widely used catalyst in the
literature and the SiNW growth using gold typically requires temperatures in the range of 600e850  C.
However, gold is a deep level impurity in silicon and therefore undesirable if the application is in
electronic devices. Metals such as Ga and In with much lower melting points have been successfully
used to catalyze the growth of SiNWs and GeNWs [59,62,63]. A VLS process using the SiCl4/H2 system is
as follows [58]. A 1 or 200 quartz tube is inserted inside a programmable furnace and a thermocouple
is inserted in the middle of the tube reactor to monitor the growth temperature. The source SiCl4 vapor
is introduced by bubbling argon through a liquid SiCl4 reservoir and H2 is admitted to obtain a preset
SiCl4/H2 ratio. A dilution line purges the system to minimize impurities such as water and oxygen.
Gaseous and solid impurities can be minimized by using suitable materials and isolation valves. The
byproduct HCl from the SiCl4 þ H2 reaction etches away any oxide layer which could be a barrier for the
catalyst alloying with silicon. The catalyst consists of a 5 nm thin film of gold applied to the wafer by ion
beam sputtering. The temperature is ramped to 925  C and maintained for 15 mins with 180 sccm of Ar

Fig. 8. Silicon nanowires grown using SiCl4/H2 and 5 nm thick gold catalyst film at 925  C (image courtesy of A. Mao).
12 M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

and 20 sccm of H2. Next, SiCl4 (0.15 mol%) is admitted for 15 min to facilitate NW growth. At the end of
this period, SiCl4 supply is turned off while maintaining the carrier gas flow during the slow cooling of
the system.
Fig. 8 shows the SiNWs from the above run which are long and curvy. A parametric study varying
SiCl4 concentration, temperature and various flow rates indicates that high SiCl4 concentrations and
high temperatures produce thinner, curvy wires. Only a very narrow set of conditions (0.04e0.1 mol%
SiCl4, 900e925  C) yield vertical nanowires which is similar to the finding by Westwater et al. [56] for
the silane/H2 system. In the latter case, silane partial pressure below 0.1 Torr and temperature in the
range of 500e600  C yielded thick, vertical wires while all other conditions yielded thinner, curvy
wires similar to those in Fig. 8.
Nanowires with diameters under 10 nm have been reported and careful characterization reveals
substantial changes in electronic properties with diameter [6]. For example, a SiNW of 1.3 nm diameter
was shown to have a bandgap of 3.5 eV with the bandgap vs. diameter behavior asymptotically
reaching the bulk value of 1.1 eV at 7.0 nm [6]. The increase in bandgap with decreasing size happens at
a larger diameter for Ge since the Bohr radius is larger than that of silicon (24.3 vs. 4.9 nm). Germanium
is attractive because of its higher intrinsic carrier mobility: mn ¼ 3900 cm2/V s, mp ¼ 1900 cm2/V s
compared to 1500 and 450 respectively for silicon. Fig. 9 shows a TEM image of a VLS-grown GeNW
with a diameter of 4 nm.
Semiconducting nanowires which are vertical on the substrate are ideal to construct vertical
surround gate (VSG) transistors. This concept has been around since the first Semiconductor Industry
Association Roadmap. Vertical transistors allow higher packing density than conventional planar
transistors, and the critical dimension (source to drain separation) is not dictated by the lithography
limit. However VSGTs fabricated until recently necessarily used silicon pillars etched out of epitaxial
films and such etched structures exhibited too poor a surface quality to be of use in device fabrication.
The NWs in contrast are single crystal structures with very good surface morphology suitable for
vertical CMOS devices. VSGTs with 6.5 nm (silicon) nanowire channel diameter have been reported to
provide on/off current ratio of 104e106 [64]. Conventional planar transistors have also been reported
using SiNWs [65]. In addition to group IV semiconductors, there have been reports on the growth of
IIIeV semiconducting nanowires such as GaAs, InP, InAs, and AlGaAs [66e69]. These studies use IIIeV

Fig. 9. TEM image of Ge quantum wire grown by VLS approach (image courtesy of X.H. Sun and B. Yu).
M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21 13

sources such as TMGa and AsH3 as in conventional MOCVD with gold colloids or gold thin film as
catalyst to guide nanowire growth.

4.2. Phase change materials

Chalcogenide materials such as Ge2Sb2Te5 (GST), GeTe, In2Se3, etc. undergo reversible phase change,
upon thermal stimulation, from an orderly single crystalline or polycrystalline C-phase to less orderly
amorphous a-phase. The reflectivity and resistivity of the two phases are substantially different
enough to represent two distinct logic states [70]. Indeed, optical data storage as in CDs and DVDs use
a phase change material (PCM) such as GST where a laser beam is used for thermal stimulation. PCM
based memory was proposed over two decades ago [70] but experienced commercialization difficulties
due to the excessive programming current needed for stimulating phase change and the thermal
interference between neighboring bits preventing scaleup [71,72].
PCM materials can be grown now in the form of nanowires using the VLS approach [73e76]. Fig. 10
shows an In2Se3 nanowire grown using VLS approach on a Si (111) wafer. The reactor consists of a 100
quartz tube inserted in a two-zone furnace. High purity In2Se3 powder (99.999%, Aldrich) is used as
source and sublimed at 950  C in the upstream section of the two-zone furnace system. The vapor is
carried by argon gas flow downstream to the growth zone maintained at 650  C. A thick film of In
(40 nm) is used as catalyst to compensate for the indium loss through evaporation since indium melts
at 157  C. The use of indium to grow indium selenide NW represents a ‘self catalytic’ approach. The
average diameter of the NWs is 60 nm and one of those NWs is shown in Fig. 10. Here, the nanowire is
contacted by metal lines patterned using e-beam lithography. The inset shows the currentevoltage
resistive characteristics of the In2Se3 nanowire with an estimated resistivity of 22 U cm at room
temperature.
PCM nanowires offer unique advantages in overcoming the difficulties faced by the PCM thin film
devices mentioned above. It is well known that the melting point of semiconductors, metals and other
materials at the nanoscale is lower than the corresponding bulk values [1,77]. Fig. 11 shows snapshots
of a video taken during the melting of a GeTe nanowire using the electron beam in TEM during imaging.
The melting point is defined as the moment when the diffraction pattern disappears. The GeTe NW

Fig. 10. In2Se3 nanowire contacted by e-beam lithography patterned metal lines. Inset shows the IeV characteristics of the nanowire
(image courtesy of Xuhui Sun and Bin Yu).
14 M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

Fig. 11. Two snapshots in a video showing melting of a GeTe nanowire. The electron beam of the TEM is used to heat the nanowire
while imaging.

(70 nm diameter) melts at 390  C which is 46% lower than the bulk melting point of 725  C [74]. When
melting is complete, a thin white shell of GeO2 (native oxide surrounding the nanowire) is left behind.
This reduction in melting point is diameter dependent and increases with decreasing diameter
[1,76,77]. Thermal conductivity of the NWs is smaller by an order of magnitude or more compared to
the bulk values. The programmable cell volume sandwiched between the top and bottom electrodes of
a memory element is also smaller with a nanowire device compared to a conventional thin film based
device. All of the above advantages together serve to reduce the thermal budget and the programming
current relative to a thin film device made with the same phase change material. It has been shown [76]
that a memory device using a 40 nm In2Se3 NW uses 11 mA programming current compared to 400 mA
for a thin film device. In addition to the geometrical advantages, there is a possibility of process-
enabled benefits as well. While conventional thin film devices have a large enough footprint, where
lithography is not the limit, denser arrays of NW devices may be fabricated using innovative self-
assembling scheme to grow the NWs in place. Ultimately a memory density of 1 Tbit/cm2 and a write
time of less than 10 ns are possible with nanowire based PRAM.
Fig. 12 shows reset and set operations of a GeTe NW-PRAM. A sequence of voltage pulses of constant
width (20 ns) but varying magnitude as shown in the inset is applied to the device. The device
resistance is measured at 0.1 V after each pulse. The crystalline material maintains its low resistance
until 2 V and shows an increase in resistance until 2.5 V when amorphous state is reached. Now the
resistance is stable at 108 U with further increase in applied voltage. The on/off ratio, i.e. ratio of

Fig. 12. Reset and set operations of a GeTe nanowire based phase change memory.
M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21 15

resistances between the two phases, is about 2000, which is large enough to distinguish between two
logic states. In the set operation, the device at the initial high resistance state is subjected to voltage
pulses of constant 20 ms width and the device resistance is measured again at 0.1 V. The resistance
begins to decrease at 0.9 V and reaches its low resistance value at 1.1 V. The power requirements of the
two operations given by V2/R are 125 mW and 11 nW respectively for the reset and set operations. This
compares very favorably with the mW power levels of the present thin film based GST devices [78].

4.3. Oxide and nitride nanowires

VLS technique has been successfully used to grow a variety of oxide nanowires such as SiO2, zinc
oxide, indium oxide, tin oxide, indium tin oxide, tungsten oxide, titanium oxide, etc. [79e85]. In most
cases, the corresponding oxides in a high purity powder form are used as a sublimation source to
generate the vapor feedstock. A reduced temperature operation is possible when the oxide powder is
mixed with graphite powder in a carbothermal reduction. For example, in the case of ZnO,

ZnOðsÞ D CðsÞ P ZnðvÞ D COðgÞ

occurs at 925  C. Since the melting point of zinc is 419  C, it rapidly evaporates and the vapor is
adsorbed into the gold catalyst particle forming a liquid alloy:

ZnðvÞ D AuðsÞ P Au L Znð[Þ

Zinc at the surface of the liquid alloy droplet is oxidized by the CO to form zinc oxide

Au L Znð[Þ D COðgÞ P Au L ZnOð[Þ D Cx Oy ðgÞ

From the liquid alloy, the oxide NW elongates according to the VLS mechanism.
Fig. 13 shows vertical ZnO nanowires grown from the process discussed above. As before,
a programmable furnace system with a 100 quartz tube is used for NW growth. A quartz boat containing
1:1 by weight mixture of ZnO powder (99.99% purity) and graphite powder (99.99% purity) is placed
upstream in the reactor tube. The substrate with a thin layer (1e3 nm) of gold is placed downstream in
the quartz tube. A constant flow (30 sccm) of argon is maintained throughout the experiment. After
15 min of equilibration, the temperature is ramped up to 925  C at a rate of 1  C/s. When the growth is
over, the entire setup is cooled to room temperature prior to removing the NW sample. The nanowire
diameter is in the range of 40e80 nm. Since the thin catalyst film breaks up randomly into droplets at

Fig. 13. Vertical zinc oxide nanowires (image courtesy of Pho Nguyen).
16 M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

the growth temperature, the nanowire diameter is not uniform. This also results in a growth rate
variation leading to different nanowire heights across the substrate. The presence of catalyst particles
at the tip of the nanowires confirms the VLS mechanism for the growth. Zinc oxide is by far the most
widely investigated material among oxide nanowires in the literature and it has potential for appli-
cations in UV LEDs, lasers, detectors, field emission devices and chemical sensors [86].
GaN, as a wide bandgap material, is the most investigated nitride nanowire due to promising
applications in optoelectronics and high power, high temperature electronics [87e90]. Indium and
aluminum nitrides can also be grown using the VLS approach [91]. Typically, vapor transport of Al, In,
or Ga is done onto the substrate with the catalyst in the presence of decomposed ammonia. The catalyst
metal may be the corresponding group III metal itself in a ‘self-catalysis’ scheme. Ammonia decom-
position is easily done with an rf or microwave plasma. Fig. 14 shows InN nanowires prepared using
such a scheme at 450  C on an amorphous quartz substrate. The nanowires are 100 nm in diameter and
a few microns long. Photoconductivity measurements indicate that the InN nanowires show a bandgap
of 0.8 eV [91].
One of the interesting applications for nanowires is thermoelectric refrigeration and power
generation [92e94]. Here energy conversion between heat and electricity is realized through the
Peltier effect where a current flow across thermocouple junctions can produce heating or cooling. In
the reverse mode, maintaining a temperature difference across a thermoelectric (TE) material induces
a current flow and generates electric power. The figure-of-merit in TE power generation and refrig-
eration called ZT is given by S2sT/K where S is the Seebeck coefficient, s is the electrical conductivity, K
is thermal conductivity and T is the temperature. The goal is to achieve a ZT greater than 3 which would
make a TE cooler competitive with conventional refrigeration. To date, a ZT value of 1 has been ach-
ieved for bulk TE materials such as bismuth telluride, various metals and semiconductors. It has been
difficult to achieve high Seebeck coefficient and electrical conductivity with a low thermal conduc-
tivity, all in one material to boost ZT values. Bulk metals are not useful since they exhibit small values of
S and high K. Semiconductors are better than metals, but bulk semiconductors suffer from low s.
Recently it has been shown that nanowires offer the best possibility to achieve high ZT values [93,94].
In quantum-confined structures, the electronic density of states is high, thus leading to a high S2s
product called the power factor. In addition, thermal conductivity of nanowires decreases with
diameter. This favorable combination of properties makes nanowires of Bi2Te3 and InSb to be promising
candidates for TE refrigeration and power conversion. Fig. 15 shows an SEM image of InSb nanowires
grown by VLS approach [92]. InSb powder (99.99%) is sublimed to generate the source vapor in
a tubular reactor and gold colloids are used as catalyst. InSb growth requires vacuum operation and

Fig. 14. Indium nitride nanowires grown by VLS approach (image courtesy of S. Vaddiraju).
M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21 17

Fig. 15. SEM image of InSb nanowires (image courtesy of Q. Ye).

possibly also a reducing environment such as hydrogen flow to eliminate the possibility of making
indium oxide wires from oxygen leaks.

5. Concluding remarks and future directions

Vaporeliquidesolid approach which is a catalyzed CVD has been widely used to grow carbon
nanotubes and various inorganic nanowires. This versatile technique is amenable for integration into
a device fabrication scheme, and in that regard, it is better than most competing techniques. While
there is an impressive literature on the growth of CNTs and INWs using this approach, numerous
challenges remain before industrial scale manufacturing and commercialization of electronics, opto-
electronics, sensors and other devices. A discussion of possible future directions is given below.
In the case of alternatives to silicon CMOS beyond Moore’s law scaling, the basic criteria for an
emerging contender include, among others, a high current drive including the ability to drive capac-
itances of interconnects of any length, integration density of greater than 1010 transistors per circuit,
better than 95% reproducibility, manufacturing costs consistent with current technology, and solutions
to technical issues including anticipated power dissipation problems with the high performance
devices. In addition, the contending technology has to be manufacturing-ready by the time of the last
generation of CMOS, which may be within a decade. It is not clear if CNT electronics can be ready by
then. The major obstacle is the inability to selectively grow semiconducting nanotubes of chosen
chirality (and hence chosen diameter and bandgap). Post-sorting from bulk samples and other ‘pick
and play’ approaches seem to be unrealistic to be adopted by the industry. Also, for a technology to be
inserted into a well-established production line, there should be a substantial process and equipment
development surrounding the new material or technology. There is a big vacuum in this regard and it
cannot be assumed that carbon nanotubes would simply replace silicon as conducting channel in an
otherwise fixed device configuration. Based on the rate of progress to date, scope of the unsolved
issues, the size and nature of the ongoing efforts, lukewarm reception from industry and the timeline
18 M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

ahead by which the technology must be ready, it is entirely unlikely that CNT-based electronics will
become a mainstream technology.
One of the most recent solutions to CNT’s chirality selection problem is graphene which is currently
receiving much attention for electronics. While this does have promise, no one as of yet knows how to
even make the graphene reliably between a pair of contacts. Exfoliation techniques, which have the
potential to produce large quantities, may not be of much value in electronic applications because of
the need to practice ‘pick and place’ for device fabrication. In situ growth by CVD or similar technique
needs to be developed before graphene can become a contender. Interestingly, all envisioned carbon-
based electronics rely on CMOS architecture with a one-to-one replacement of silicon with CNT.
SWCNTs have interesting morphology and properties and as-grown structures may be amenable to
other types of computing such as neural architecture. However, there is negligible effort in such
a direction and also on the use of CNTs for spin-based electronics.
Among all nanomaterials, nanowires e particularly silicon and germanium e offer promise for logic
devices. An inherent advantage is that industry will not view them as exotic materials since these
nanowires are just one-dimensional incarnation of a familiar material. This would allow the use of
much of the past material and process development in terms of dielectrics, metal contacts, etc. What is
urgently needed from the research community is controlled growth of nanowires in short segments,
vertical or horizontal. Unfortunately, much of the literature on any type of nanowire always focuses on
how long they can be grown even though it is not clear what application, if any, requires long wires. In
keeping up with CMOS scaling, SiNWs and GeNWs well under 100 nm (long or tall) are needed.
Achieving this in itself is not the issue, but processing a device, especially VSGT, with a critical
dimension of 60 nm or less requires substantial process development. While early NW device publi-
cations focused on quick fabrication of few devices matching critical dimensions of the 1990s (1e
2 mm), attention must turn to realistic length scales and associated process development. This is
unlikely to be a serious issue in industrial labs and fabs since there has already been successful
exploration into non-traditional small CMOS devices such as double-gate structures, FINFET, etc. in
recent years [95].
The picture on the memory side of electronics is not much different either for nanomaterials. The
need for scalable, dense, nonvolatile memory technology is clear as the Flash memory is facing serious
issues in terms of process complexity, scalability, cost and endurance. There are several alternatives
under consideration such as MRAM, FeRAM and PRAM all of which show much higher endurance
[95,96]. CNT-based memory with a cross bar architecture uses electromechanical deflection of the
nanotube for distinguishing the logic states [97]. There is not much literature in this field and any
progress made to date is mostly proprietary work within one or two companies. Scalability, reliability
and endurance are all serious issues with this technology and much work needs to be done to establish
the viability of CNT memory technology. Interestingly, since there is no charge transport involved, CNT-
based electromechanical switch will be a radiation-immune memory as with the case of PRAM.
In the other three emerging alternatives MRAM, FeRAM and PRAM, nanowires and nanotubes have
not yet played a prominent role. Interest in PRAM now is very high, not only because of the finite time
left for Flash scaling but also because much more is known about GST and other chalcogenide materials
than in 1968 when PRAM was proposed [70]. Programming currents have come down significantly
since then. As discussed before, NW based PRAM shows even more potential in terms of scalability and
reduced programming current. At this writing, however, it is not clear if the nanowire approach is
under consideration in any of the memory companies involved in PRAM.
One of the most discussed CNT applications in the literature involves field emission for large flat
panel displays for television, indoor/outdoor advertisement and similar needs. Emission characteristics
of SWCNTs, MWCNTs, CNFs and related structures have been studied exhaustively and the figures-
of-merit such as turn-on voltage, current density, etc. have been impressive (see Ref. [46] and refer-
ences therein). Much of the published data is from small pieces of wafers and therefore offers no
information on emission site density, manufacturability and reliability. Commercial efforts do not
appear to use in situ CNT growth on each pixel using CVD or PECVD; large scale commercial equipment
for growth is not available now, though large scale CVD/PECVD reactors are available in other industries
for manufacturing LCD and solar panels. Instead, bulk-produced nanotubes mixed with a binder are
applied by screen printing which yields protruding CNT ends at the pixels. What we know is, after years
M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21 19

of intensive research, there are no CNT-based flat panels in the market yet. In the meantime, substantial
progress has been made on competing technologies CNT displays hope to replace, namely the LCD and
plasma displays. The prices of the latter have come down so much that it is not clear if there would ever
be a profitable insertion point for the CNT displays of large size. On the other hand, some niche markets
for small displays may still be open. The literature also features field emission from various inorganic
nanowires [4]; however the relative merits of any of these materials are not clear. Careful, controlled
measurements under identical conditions are needed to draw meaningful conclusions on material
choice for field emission from all the available nanowires and CNTs.
The opportunities and future directions for CNTs and INWs in other areas such as optoelectronics,
lasers, detectors, LEDs, chemical and biosensors, instrumentation, etc. are much more promising and
clear (see Table 2 for a summary of applications for INWs). This is in part due to the absence of large
incumbent technologies in these fields waiting to be replaced in the foreseeable future. The pace is
dictated by the evolution of the technology itself rather than an arbitrary time frame handed down by
something like Moore’s law. For example, commercial chemical sensors now are based on tin oxide thin
film devices or polymeric sensors where the polymer film swells upon adsorption of a gas or vapor [52].
There are opportunities for CNT or INW based sensors to eclipse these devices in terms of sensitivity,
size, weight, power consumption and room temperature operation. Future work should include
approaches for selective discrimination of the analyte of interest and application development since
availability of low power, reliable sensors can open up new markets in chemical, petroleum, food
processing, biomedical, security and other industries [52]. Similarly, the use of CNTs and SiNWs for
biosensing also has appeal over current technologies due to high sensitivity and possibilities of large
wafer scale fabrication. Electrical signal transduction following probeetarget interaction allows on-
chip fabrication of the sensor with microfluidics together.
Though CNT field emission for large scale flat panel displays may face manufacturing issues related
to large area uniformity, etc. and pressure from competing technologies as mentioned before, field
emission at current densities above 500 mA/cm2 has numerous applications in instrumentation. For
example, CNT-based X-ray tubes are under investigation for airport baggage screening and medical
imaging [98e100]. The technical issues here include reliability and life time, and demonstration of
a compact source including the focusing optics. When these issues are addressed, products far superior
to the present thermionic emission based imaging devices are expected. The current devices are large,
consume high power, require cooling and may require rotation of the source for imaging large objects.
Nanowires of various materials appear to have unlimited potential in optoelectronics such as LED,
multi-wavelength IR detectors, UV detectors, lasers, etc. [4]. Current focus is on demonstration of the
possibilities and basic growth and characterization. Future work should include understanding growth
mechanism, reproducible growth techniques, large wafer growth, and peripheral process development
for device fabrication. Though there is an extensive literature on the VLS growth, a major challenge
remains in terms of selection of low melting metal catalysts for enabling device fabrication. A major
proportion of the literature deals with gold which can be effective as a low temperature catalyst but
more importantly it can create a deep level trap in silicon. The latter is an issue if any integration with

Table 2
Application summary for inorganic nanowires.

Material Application
Silicon Electronics, chemical and biosensors
Germanium Electronics, IR detectors
Tin oxide Chemical sensors
Indium oxide Chemical sensors, biosensors
Indium tin oxide Transparent conductive film in display electrodes, solar cells, organic light emitting diodes
Zinc oxide UV laser, field emission device, chemical sensor
Copper oxide Field emission device
Wide bandgap nitrides (GaN) High temperature electronics, UV detectors and lasers, automotive electronics and sensors
Boron nitride Insulator
Indium phosphide Electronics, optoelectronics
Zinc selenide Photonics (Q-switch, blue-green laser diode, blue-UV photodetector)
Copper, tungsten Electrical interconnects
20 M. Meyyappan / Progress in Crystal Growth and Characterization of Materials 55 (2009) 1e21

silicon electronics or MEMS is desired. Finally, there has not been much work on the reactor-scale
modeling taking into account the kinetics, thermodynamics, fluid flow, heat and mass transfer. This is
partly due to the fact that wafer scale growth of any of these materials is not common yet and most
published works deal with 1 cm2 wafer pieces or similar small sizes. There is a reasonable level of
modeling at the growth level, particularly for carbon nanotubes. This knowledge needs to be combined
with the reactor level issues mentioned above as has been done previously in the case of other
materials such as silicon, IIIeV and diamond thin films.

Acknowledgement

The author acknowledges his present and former colleagues from NASA Ames Research Center: Alan
Cassell, Bin Chen, Lance Delzeit, Jing Li, Jun Li, Y. Lu, Aaron Mao, Cun-Zheng Ning, Cattien Nguyen, Pho
Nguyen, H.T. Ng, Quoc Ngo, Xuhui Sun, Sreeram Vaddiraju, Laura Ye, and Bin Yu for valuable discussions
and providing some of the images used in this work.

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