Nanowires: Dept of Biotechnology, RVCE

NANOWIRES
Dept of Biotechnology, RVCE Page 1

1. INTRODUCTION

A nanowire is a nanostructure, with the diameter of the order of a nanometer (10
9
meters). Alternatively, nanowires can be defined as structures that have a thickness or diameter
constrained to tens of nanometers or less and an unconstrained length. At these scales, quantum
mechanical effects are important which coined the term "quantum wires".

Nanowires are especially attractive for nanoscience studies as well as for nanotechnology
applications. Because of their unique density of electronic states, nanowires in the limit of small
diameters are expected to exhibit significantly different optical, electrical, and magnetic
properties. Nanowires have been shown to provide a promising framework for applying the
bottom-up approach for the design of nanostructures.

Bottom-up assembled nanoscale electronics could provide unparalleled speed, storage, and size
reductions and hold the promise of powering future electronic devices that can outperform
existing devices and open up totally new opportunities. A bottom-up approach, where functional
electronic structures are assembled from chemically synthesized, well-defined nanoscale
building-blocks, has the potential to go far beyond the limits of top-down technology by defining
key nanometer-scale metrics through chemical synthesis and subsequent assemblynot just by
lithography.

Central to the bottom-up approach are the nanoscale building blocks. One-dimensional (1D)
nanostructures represent the smallest dimension structure that can efficiently transport electrical
carriers, and thus are ideally suited to the critical and ubiquitous task of moving and routing
charges, which constitute information, in nanoelectronics. In addition, 1D nanostructures can
also exhibit critical device function, and thus can be exploited as both the wiring and device
elements in future architectures for functional nanosystems. In this regard, two material classes,
semiconductor nanowires (NWs) and carbon NTs have shown particular promise.
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2.TYPES OF NONOWIRES

Metallic nanowires: Metal nanowires are made from nickel(Ni), platinum(Pt), gold(Au).

Semiconducting nanowires: These wire are comprised of silicon, indium phosphide,
gallium nitride.

Insulating nanowires: These wires made from silicon dioxide(SiO
2
) or titanium
dioxide(TiO
2
)

Molecular nanowires: To create a molecular nanowire, the process involves repeating
organic or inorganic molecular units in a particular format.

Oxide nanowires: Made from zinc oxide and copper oxide.

multi-segment nanowires

3. HOW NANOWIRES ARE MADE?

There are varying methods used to create nanowires. The most common involve either growing
them or using DNA as a template. For the latter method, a solution
containing the desired metal is mixed with DNA and then exposed
to UV light. When exposed, the metal in the mixture bonds to the
DNA and forms a microscopic wire, a nanowire. Its width is
dependent upon how concentrated the solution of the metal is. The
more concentrated the metal solution, the wider the nanowire
likewise, the less concentrated, the thinner the wire will be.

4. SYNTHESIS OF NANOWIRES

There are two basic approaches to synthesizing nanowires: top-down and bottom-up. A top-
down approach reduces a large piece of material to small pieces, by various means such as
lithography or electrophoresis. A bottom-up approach synthesizes the nanowire by combining
constituent adatoms.
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Many techniques have been developed in the synthesis and formation of one-dimensional
materials, like nanowires. These techniques can be generally grouped into four categories:
1- Spontaneous growth:

a. Evaporation condensation
b. Dissolution condensation
c. Vapor (solution)-liquid-solid growth (VLS or SLS)

d. Stress-induced re-crystallization

2- Template-based synthesis:

a. Electrochemical deposition
b. Electrophoretic deposition
c. Colloid dispersion, melt, or solution filling
d. Conversion with chemical reaction
3- Electro-spinning

4- Lithography

Spontaneous growth, template-based and electro-spinning syntheses are considered bottom-up
approaches, whereas lithography is a top-down technique.

Spontaneous Growth

Spontaneous growth is a process driven by the reduction of Gibbs free energy or chemical
potential. The reduction of Gibbs free energy is commonly realized by phase transformation or
chemical reaction or the release of stress. For the formation of nanowires or nanorods,
anisotropic growth is required (i.e. the crystal along a certain orientation faster than other
directions). Uniformly sized nanowires (i.e. the same diameter along the longitudinal direction of
a given nanowire) can be obtained when crystal growth proceeds along one direction, where as
there is no growth along other direction.
Evaporation Condensation

Evaporation-condensation process is also referred to as vaporsolid (VS) techniques. Nanowires
and nanorods grown by this method are commonly single crystals with fewer imperfections. The
formation of nanowires or nanorods is due to the anisotropic growth. Several mechanisms are
known to result in anisotropic growth, but the general idea is that the different facets in a crystal
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have different growth rates. For example mercury nanowires are grown by this method, with a
condensation temperature of -50 C under vacuum and the axial growth rate is approximately 1.5
mm /sec under a super-saturation condition.

Dissolution Condensation

This process differs from Evaporation-condensation in growth media. In this method, the growth
species first dissolve into a solvent or a solution, and then diffuse through the solvent or solution
and deposit onto the surface resulting in the growth of nanorods or nanowires. The nanowires in
this method can have a mean length of <500 nm and a mean diameter of ~60 nm.
Vapor-Liquid-Solid growth (VLS)

A common technique for creating a nanowire is Vapor-Liquid-Solid (VLS) synthesis. This
process can produce crystalline nanowires of some semiconductor materials. It uses as source
material either laser ablated particles or a feed gas such as silane. VLS synthesis requires a
catalyst. For nanowires, the best catalysts are liquid metal (such as gold) nanoclusters, which can
either be self-assembled from a thin film by dewetting, or purchased in colloidal form and
deposited on a substrate.

Figure 1: Model of VLS growth

Insert a substrate with gold catalyst particles into the growth chamber. We then heat the substrate
while introducing a vapor of metal-organic chemicals. These decompose on the growth substrate
leaving free metal atoms, which alloy with the gold catalyst particle. Upon saturation, the
catalyst nucleates epitaxial growth of a nanowire. With this mechanism we can achieve a high
degree of control over the dimensions of the nanowire by controlling the diameters of the seed
particles and the growth time.
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Template Based Synthesis

This is the very general method and can be used in fabrication of nanorods, nanowires, and
nanotubes of polymers, metals, semiconductors, and oxides. Various templates with nano-size
channels have been explored for template growth of nanorods and nanotubes. The porous
membranes are fabricates with different methods. The pores are arranged in a regular hexagonal
arrays and densities as high as 1011 pores/cm2 can be achieved. Pore size ranging from 10 nm to
100 mm can be achieved.

Electrochemical Deposition

This method can be understood as a special electrolysis resulting in the deposition of solid
material on an electrode. This method is only applicable to electrically conductive materials such
as metals, alloys, semiconductors, and electrical conductive polymers. This is a self-propagating
process. It is a widely used approach to fabricate nanowires which based on various templates
and include negative, positive, and surface step templates.
Negative Template Method

This method use prefabricated cylindrical nanopores in a solid material as templates. By
depositing metals into the nanopores, nanowires with a diameter predetermined by the diameter
of the nanopores are fabricated. There are several ways to fill the 3 nanopores with metals or
other materials to form nanowires, but the electrochemical method is a general and versatile
method. If one dissolves away the host solid material, free-standing nanowires are obtained.
Obviously, the diameter of the nanowires is determined by the geometrical constraint of the
pores rather than by elegant chemical principles. However, it is one of the most successful
methods to fabricate various nanowires that are difficult to form by conventional lithographic
process. Fabrication of suitable templates is clearly a critical first step. To date, various methods
have been developed to fabricate various negative templates. All of these materials contain a
large number of straight cylindrical nanopores with a narrow distribution in the diameter of
nanopores.
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Figure 2: Model of template base synthesis

Using the membrane templates previously, nanowires of different types have been fabricated.
These nanostructures can be deposited into the pores by either electrochemical deposition or
other methods, such as chemical vapor deposition (CVD), chemical polymerization, electroless
deposition, or by sol-gel chemistry. Electrodeposition is one of the most widely used methods to
fill conducting materials into the nanopores to form continuous nanowires with large aspect
ratios. One of the great advantages of the electrodeposition method is the ability to create highly
conductive nanowires. This is because electrodeposition relies on electron transfer, which is the
fastest along the highest conductive path.
Structural analysis showed that the electrodeposited nanowires tend to be dense, continuous, and
highly crystalline in contrast to other deposition methods. Another important advantage of the
electrodeposition method is the ability to control the aspect ratio of the metal nanowires by
monitoring the total amount of passed charge. This is very important for many applications. For
example, the optical properties of nanowires are critically dependant on the aspect ratio.
Nanowires with multiple segments of different metals in a controlled sequence can also be
fabricated by controlling the potential in a solution containing different metal ions.
Electrodeposition often requires one to deposit a metal film on one side of the freestanding
membrane to serve as a working electrode on which electrodeposition takes place. This film has
to completely seal the pores on one side. The opposite side of the membrane is exposed to an
electrodeposition solution, which fills up the pores and allows metal ions to reach the metal film.
This is a form of support which also prevents one form breaking the fragile membrane during
handling.
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Positive Template Method

The positive template method uses wire-like nanostructures, such as DNA and carbon nanotubes
as templates, and nanowires are formed on the outer surface of the templates. Unlike negative
templates, the diameter of the nanowires is not restricted by the template sizes and can be
controlled by adjusting the amount of materials deposited on the templates. By removing the
templates after deposition, wire-like and tube-like structures can be formed. DNA is an excellent
choice as a template to fabricate nanowires because its diameter is ~2 nm and its length and
sequence can be precisely controlled. The general procedure is first to fix a DNA strand between
two electrical contacts. The DNA then is exposed to a solution containing some ions. The ions
bind to DNA and are then form some nanoparticles decorating along the DNA chain. In the last
step, the nanoparticles are further developed into a nanowire using a standard photographic
enhancement technique.

Figure 3:DNA base template (a)DNA bridge connecting two electrodes, (b)Ion loaded DNA bridge, (c)Fully developed wire on DNA

Electrophoretic Deposition

This method differs from electrochemical deposition in several aspects. In this method, the
deposit need not be electrically conductive, so this method is particularly useful for oxide
nanowires such as SiO2, TiO2, Bi2O3, etc. Nanosize particles in colloidal dispersions are
typically stabilized by electrostatic mechanisms. Actually over the surface of nanoparticles
develops an electrical charge via some chemical techniques. This combination is typically called
Counter-Ion. Upon application of an external electric filed to a system of charged nanosize
particle system, the particles are set in motion in response to the electric filed. This type of
motion is referred to as electrophoresis. The rest of this technique is the same as electrochemical
deposition.
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Surface Step-Edge Templates

Atomic-scale steps on a crystal surface can be used as templates to grow nanowires. The method
takes the advantage of the fact that deposition of many materials on the surface often starts
preferentially at defect sites, such as surface step-edges. For this reason, the method is sometimes
called step edge decoration. Using the step edges of highly oriented graphite as template,
fabricates nanowires by electrodeposition. Other techniques such as physical vapor deposition
(PVD) method also used. But the problem is that these nanowires can not be easily removed
from the surface on which they are deposited, which can be a serious limit for some applications.
Anyhow, there are some techniques to separate the nanowires form the edge of the substrate
crystal.

Figure 4: surface step-edge template (a)step-edge graphite, (b)Electro deposition of metal oxide, (c) formation of nanowire at the edges.

Electro-spinning

Electro-spinning occurs when the electrical forces at the surface of a polymer solution or melt
overcome the surface tension and cause an electrically charged jet to be ejected. When the jet
dries or solidifies, an electrically charged fiber remains. This fiber can be directed or accelerated
by electrical forces and then collected in sheets or other useful geometrical forms.
Lithography

Various lithography techniques have been explored in the fabrication of nanowires, such as
electron beam lithography, ion beam lithography, X-ray lithography. Nanowire with diameters
less than 10 nm and an aspect ratio of 100 can be readily prepared.
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5. NANOWIRE APPLICATIONS.

Perhaps the most obvious use for nanowires is in electronics. Some nanowires are very good
conductors or semiconductors, and their miniscule size means that manufacturers could fit
millions more transistors on a single microprocessor. As a result, computer speed would increase
dramatically.

Nanowires may play an important role in the field of quantum computers. A team of researchers
in the Netherlands created nanowires out of indium arsenide and attached them to aluminum
electrodes. At temperatures near absolute zero, aluminum becomes a superconductor, meaning it
can conduct electricity without any resistance. The nanowires also became superconductors due
to the proximity effect. The researchers could control the superconductivity of the nanowires by
running various voltages through the substrate under the wires.

Nanowires may also play an important role in nano-size devices like nanorobots. Doctors could
use the nanorobots to treat diseases like cancer. Some nanorobot designs have onboard power
systems, which would require structures like nanowires to generate and conduct power.

Using piezoelectric material, nanoscientists could create nanowires that generate electricity from
kinetic energy. The piezoelectric effect is a phenomenon certain materials exhibit -- when you
apply physical force to a piezoelectric material, it emits an electric charge. If you apply an
electric charge to this same material, it vibrates. Piezoelectric nanowires might provide power to
nano-size systems in the future, though at present there are no practical applications.

There are hundreds of other potential nanowire applications in electronics. Researchers in Japan
are working on atomic switches that might some day replace semiconductor switches in
electronic devices. Scientists with the National Renewable Energy Laboratory hope that coaxial
nanowires will improve the energy efficiency of solar cells. Because we are still learning about
the properties of nanowires and other nanoscale structures, there could be thousands of
applications we haven't even considered yet.
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Nanowires in Medicine

Not all nanowire applications are in the field of electronics. At the University of Arkansas,
researchers are using nanowires to coat titanium implants. Doctors have discovered that muscle
tissue sometimes doesn't adhere well to titanium, but when coated with the nanowires, the tissue
can anchor itself to the implant, reducing the risk of implant failure.

Scientists at the Gladstone Institute of Cardiovascular Disease are experimenting with nanowires
and stem cells. They hope that by running an electric current through a nanowire into the stem
cell they can direct how the cell differentiates.

Some other uses of nanowires include:

Data storage/transfer - transfer data up to 1,000 times faster, and store data for as long as

100,000 years without degradation

Batteries/generators - tiny, efficient solar panels, turning light into energy, able to hold 10
times the charge of existing batteries
Transistors

LEDs

Optoelectronic devices

Biochemical sensors

Heat-pumping Thermoelectric devices
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6. CONCLUSION

Advances:

Synthesis of nano scale building blocks with precisely controlled chemical composition,
physical dimension, and electronic, optical properties
Some strategies for the assembly of building blocks into increasingly complex structures

New nano device concepts that can be implemented in high yield by assembly
approaches
Nanowires are simply very small wires that will be able to greatly reduce the size of
electronic devices while allowing us to increase the efficiency of those devices.

They are not widely used yet because they are still being developed in laboratories and
have not moved to manufacturing plants.

The most apparent impact this will have on society would be the increase of storage
space for mp3 players, computers, and phones without increasing size.
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7. REFERENCES

Holmes, Justin D.; Johnston, Keith P.; Doty, R. Christopher and Korgel, Brian A.,
Control of thickness and orientation of solution-grown silicon nanowires. Science (2000),
287(5457), 1471-1473.

Heitsch, Andrew T.; Akhavan, Vahid A.; Korgel, Brian A., Rapid SFLS Synthesis of Si
Nanowires Using Trisilane with In situ Alkyl-Amine Passivation. Chemistry of Materials
(2011), 23(11), 2697-2699.
Hanrath, Tobias and Korgel, Brian A., Supercritical fluid-liquid-solid (SFLS) synthesis
of Si and Ge nanowires seeded by colloidal metal nanocrystals. Advanced Materials
(2003), 15(5), 437-440.
A. T. Tilke et al. (2003). Physical Rev. B 68: 075311.

Wee Welding with Nanosolder, Chemical & Engineering News, 86, 51 (22 Dec. 2008).

Cold welding of ultrathin gold nanowires, Nature Nanotechnology, Y. Lu et al. 5, (14

Feb. 2010, doi:10.1038/nnano.2010.4), p. 213-224

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