SYNTHESIS OF NANOWIRES

Prepared by: Kanika Misra Guide: Dr. Bina. R. Sengupta

Introduction
A nanowire is a structure, with the diameter of the order of a nanometer (109 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". Typical nanowires exhibit aspect ratios (length-to-width ratio) of 1000 or more. They are often referred to as one-dimensional (1-D) materials. Nanowires have many interesting properties that are not seen in bulk or 3-D materials. This is because electrons in nanowires are quantum confined laterally and thus occupy energy levels that are different from the traditional continuum of energy levels or bands found in bulk materials. There are two basic approaches of synthesizing nanowires: top-down and bottom-up approach. In a top-down approach a large piece of material is cut down to small pieces through different means such as lithography and electrophoresis. Whereas in a bottom-up approach the nanowire is synthesized by the combination of constituent ad-atoms. Most of the synthesis techniques are based on bottom-up approach. Nanowire structures are grown through several common laboratory techniques including suspension, deposition (electrochemical or others), and VLS growth.

2 1. A. T. Tilke et al. (2003). Physical Rev. B 68: 075311.

Template assisted nanowire growth

Conceptually simple and intuitive way to synthesize nanowires. Templates contain very small cylindrical pores or voids within the host material, and the empty spaces are filled with the chosen material, which adopts pore morphology, to form nanowires.

Templates frequently used for nanowire synthesis include anodic alumina (Al2O3), nano-channel glass, ion track-etched polymers and mica films. Porous anodic alumina templates are produced by anodizing pure Al films in various acids. Under carefully chosen anodization conditions, the resulting oxide film possesses a regular hexagonal array of parallel and nearly cylindrical channels, as shown in Fig. 1. The self-organization of the pore structure in an anodic alumina template involves two coupled processes: pore formation with uniform diameters and pore ordering. Depending on the anodization conditions, the pore diameter can be systematically varied from < 10nm up to 200nm with a pore density in the range of 109-1011 pores/cm2.
M. S. Dresselhaus Y.M. Lin, O. Rabin, M.R. Black, G. Dresselhaus. NANOWIRES, 4 ,(January 2, 2003)

Fig 1

Fig 2

Template assisted synthesis by pressure injection

Employed for fabricating highly crystalline nanowires from a low-melting point material or

when using porous templates with robust mechanical strength. The nanowires are formed by pressure injecting the desired material in liquid form into the evacuated pores of the template. The pressure P required to overcome the surface tension for the liquid material to fill the pores with a diameter dW is determined by the Washburn equation dW = -4 cos /P where is the surface tension of the liquid, and is the contact angle between the liquid and the template. To reduce the required pressure and to maximize the filling factor, some surfactants are used to decrease the surface tension and the contact angle. Nanowires produced by the pressure injection technique usually possess high crystallinity and a preferred crystal orientation along the wire axis.
XRD patterns of bismuth/anodic alumina nano-composites with average bismuth wire diameters of (a) 40 nm, (b) 52 nm, and (c) 95nm

4 M. S. Dresselhaus Y.M. Lin, O. Rabin, M.R. Black, G. Dresselhaus. NANOWIRES, 4 ,(January 2, 2003)

Electrochemical deposition
In the electrochemical methods, a thin conducting metal film is first coated on

one side of the porous membrane to serve as the cathode for electroplating. In the electrochemical deposition process, the chosen template has to be chemically stable in the electrolyte during the electrolysis process. Particle track-etched mica films or polymer membranes are typical templates used in the simple dc electrolysis. In ac electrochemical deposition, although the applied voltage is sinusoidal and symmetric, the current is greater during the cathodic half-cycles, making deposition dominant over the etching, which occurs in the subsequent anodic half-cycles. In this fashion, metals, such as Co and Fe, and semiconductors, such as CdS, have been deposited into the pores of anodic aluminum oxide templates. Furthermore, single-crystal Pb , Ag nanowires can be formed by pulse electrodeposition under over-potential conditions. The use of pulse currents is believed to be advantageous for the growth of crystalline wires because the metal ions in the solution can be regenerated between the electrical pulses and, therefore, uniform deposition conditions can be produced for each deposition pulse.
(b) SEM image of a Bi2Te3 nanowire array composite along the wire axis (Sander et al., 2002).

(a) SEM image of a Bi2Te3 nanowire array in cross section showing a relatively high pore filling factor. 5

M. S. Dresselhaus Y.M. Lin, O. Rabin, M.R. Black, G. Dresselhaus. NANOWIRES, 4 ,(January 2, 2003)

 One advantage of the electrochemical deposition technique is the possibility of fabricating multilayered structures within nanowires. By varying the cathodic potentials in the electrolyte which contains two different kinds of ions, different metal layers can be controllably deposited. In this fashion, Co/Cu multi-layered nanowires have been synthesized. Figure shows TEM images of a single Co/Cu nanowire of about 40nm in diameter. The light bands represent Co-rich regions and the dark bands represent Cu-rich layers. This electrodeposition method provides a low-cost approach to prepare multi-layered 1D nanostructure.

In contrast to nanowires synthesized by the pressure injection method, nanowires fabricated by the electrochemical process are usually polycrystalline, with no preferred crystal orientations, as observed by XRD studies. However, some exceptions exist. For example, polycrystalline CdS nanowires, fabricated by an ac electrodeposition method in anodic alumina templates possibly have a preferred wire growth orientation along the c-axis.

(a) TEM image of a single Co(10 nm)/Cu(10 nm) multilayered nanowire. (b) A selected region of the sample at high magnification (Piraux et al., 1994).

Surfactants are also used with electrochemical deposition when necessary.

Vapor deposition
Vapor deposition of nanowires includes physical vapor deposition (PVD), chemical vapor deposition (CVD), and metallorganic chemical vapor deposition (MOCVD). In the physical vapor deposition technique, the material to be filled is first heated to produce a vapor, which is then introduced through the pores of the template and cooled to solidify. Compound materials that result from two reacting gases have also be prepared by the chemical vapor deposition (CVD) technique.

Figure shows the SEM image and XRD spectrum of InN nanowires synthesized using MOCVD.

Figure shows that source Si is condensed on the catalyst until it reaches a critical diameter as shown in Figures 4 (b) and (c) after which, the nanowire grows at the saturation point of the catalyst alloy

1. Y. Civale, L. K. Nanver, P. Hadley, E. J. G. Goudena, Aspects of Silicon Nanowire Synthesis by Aluminum-Catalyzed Vapor-LiquidSolid Mechanism, ACS, 692-695 7 2. M. S. Dresselhaus Y.M. Lin, O. Rabin, M.R. Black, G. Dresselhaus. NANOWIRES, 4 ,(January 2, 2003)

Thermal Annealing
The thermal annealing method of synthesizing nanowires is a very simple method because it does not involve complex mechanism for synthesis compared to CVD method.

Gas Temperature controlled Furnace

Schematic for thermal annealing process

For the synthesis of gold-silica p-type silicon substrate etched with hydrofluoric acid and coated with about 50 nm of gold by sputtering gold onto the substrate surface in order to maintain uniformity. A thermal annealing temperature of 1100 degrees C for 1 hour is required to synthesize goldsilica nanowire in the diameter range of 30-150 nm, they also recommend a 3 % hydrogen/argon gas ambient surrounding to eliminate oxidation of nanowire. The temperature required for the annealing process for various nanowires can be obtained from the appropriate phase diagram.

Roger Prasad, Dr. Zhen Guo, Synthesis and Characterization of Nanowires ,MatE 297 ( May 10, 2006)

VLS Mechanism
Phase diagram is usually used to determine the favorable conditions for growth of nanowires. Melting temperature for gold is lower than silicon. In order to grow the nanowire a temperature between the two melting points is selected for the evaporation segment and a lower temperature for the synthesis segment that favors condensation into the gold-silicon alloy. The proposed growth mechanism involves the absorption of source material from the gas phase into a liquid droplet of catalyst Upon supersaturation of the liquid alloy, a nucleation event generates a solid precipitate of the source material. This seed serves as a preferred site for further deposition of material at the interface of the liquid droplet. The VLS mechanism in Figure shows that the growth happens when silicon diffuses into the alloy puddle which increasing the Au-Si interface, this enhances melting of Si into the alloy. The composition of Au-Si in the nanowire can be selected by changing the temperature as shown in Figure. The advantage to using a mechanism utilizing catalyst is that the direction and location of growth of nanowire can be controlled .

1. 2.

M. S. Dresselhaus Y.M. Lin, O. Rabin, M.R. Black, G. Dresselhaus. NANOWIRES, 4 ,(January 2, 2003) Roger Prasad, Dr. Zhen Guo, Synthesis and Characterization of Nanowires ,MatE 297 ( May 10, 2006)

Methods for Growth of CNTs

Furnace at 1200 rC Water-cooled copper collector

Ar gas
Nanotube growing along tip of collector Laser Graphite target

Laser Ablation Process

Formation of nanotubes
Power Supply

Note: The target may be made by pressing Si powder mixed with 0.5% iron.

Water in

Water out

in
Water

out

out

Water in

Arc-Discharge System
graphite, cathode
auto pressure controller

He

mass flow controller

graphite
anode

pump
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Applications
Material
Ag Au Bi Ca B6 CdS CdSe Cu Fe

Growth technique
DNA template, redox template, pulsed ECD Template, EDC Stress induced, vapor phase, ECD template, pressure injection Thermal process Liq. phase, recrystallization template, ac EDC Liq, phase, redox template, ac EDC Vapour deposition template, EDC template, shadow deposition

Applications
Barcode tags, interconnects in electronic circuits, nanoelectrodes Optical switching, barcode tags, colorimetric markers or sensors Thermoelectric, nano-optoelectronic, cryogenic cooling applications Aerospace applications Laser LEDs & optical devices based on nonlinear properties Solar cells, optic applications Sensing of important molecules PEM fuel catalyst applications, spintronics devices, high density data storage, environmental remediation applications FET, logic gates, super current switches Rectifiers, optoelectronic application Visible optoelectronics, lasering action
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GaP/GaAs GaAs GaN

VLS Template, liq,/vapor OMVCD Hydroxy vapour epitaxy, template, VLS

Contd

Material
InP MnO2 Mo Ni PbSe Pd Se

Growth Mechanism
VLS Template free synthesis Step decoration, EDC redox Template, EDC Liquid phase Step decoration, EDC Liq. Phase, recrystallization template, pressure injection VLS, laser ablation VLS, oxide assisted low T VLS Epitaxal growth(template) Template, vapor phase template, EDC VLS template, ECD, CVD

Applications
P-n jnc diodes Lithium battery applications Field emission, Li-ion battery/ pseudo capacitor applications Barcode tags, magnetic info storage Photovoltaic cells Barcode tags, nanosensors for detecting H2 Light/temp sensors, rectifiers, photocopting m/c, inorganic pigments & piezoelectric actuators Flat panel display, pH sensor, microelectronics Li-ion batteries, dye sentitized solar cells, gas sensors Gas sensing, FET Accoustic transducers, sensors & actuators, lasering actions
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Si SnO2 Zn ZnO

1. 2.

M. S. Dresselhaus Y.M. Lin, O. Rabin, M.R. Black, G. Dresselhaus. NANOWIRES, 4 ,(January 2, 2003) Y. Xia,P. Yang, Y. Yin, Y. Sun, Y. Wu, B. Mayer, B. Gates, F. Kim, H. Yan, 1-D Nanostuctures: synthesis, characterization & applications, Adv. Mater., 2003,15,no. 5, (March 4)