R.V.

COLLEGE OF ENGINEERING BANGALORE 560059

(Autonomous Institution Affiliated to VTU,Belgaum)

Carbon Nanotube Synthesis by Chemical Vapour Deposition Seminar Report

Submitted By Rahul kumar 1RV08CH026

Introduction to Nanotubes
Carbon nanotubes are molecular-scale tubes of graphitic carbon with outstanding properties. They are among the stiffest and strongest fibres known, and have remarkable electronic properties and many other unique characteristics. For these reasons they have attracted huge academic and industrial interest, with thousands of papers on nanotubes being published every year. Commercial applications have been rather slow to develop, however, primarily because of the high production costs of the best quality nanotubes. History The current huge interest in carbon nanotubes is a direct consequence of the synthesis of buckminsterfullerene, C60, and other fullerenes, in 1985. The discovery that carbon could form stable, ordered structures other than graphite and diamond stimulated researchers worldwide to search for other new forms of carbon. The search was given new impetus when it was shown in 1990 that C60 could be produced in a simple arc-evaporation apparatus readily available in all laboratories. It was using such an evaporator that the Japanese scientist Sumio Iijima discovered fullerene-related carbon nanotubes in 1991. The tubes contained at least two layers, often many more, and ranged in outer diameter from about 3 nm to 30 nm. They were invariably closed at both ends. Structure The bonding in carbon nanotubes is sp, with each atom joined to three neighbours, as in graphite. The tubes can therefore be considered as rolled-up graphene sheets (graphene is an individual graphite layer). There are three distinct ways in which a graphene sheet can be rolled into a tube.

Nanotube Classification
Carbon nanotubes are tubular carbon molecules provided with very particular properties. Their structure is similar to fullerene; but while the fullerene's molecules form a spherical shape, nanotubes are cylindrical structures with the ends covered by half a fullerene molecule. Nanotube diameter is of the order of a few nanometers, while their length can be of the order of several millimeters. The Physical Structure of Carbon Nanotubes The physical properties of nanotubes make them potentially useful in nanometric scale electronic and mechanical applications, since they show unusual strength, unique electrical properties and extremely high thermal conductivity. The chemical bonding between carbon atoms inside nanotubes is always of sp2 type, the same that we find in graphite, and provides them their unique strength. Moreover, they align themselves into ropes held together by the Van der Waals force and can merge together under high pressure, trading some sp2 bonds to sp3 and producing very strong wires of nanometric lateral dimension. The Two Types of Carbon Nanotubes: Single-Walled (SWNT) and Multi-Walled (MWNT) Several types of nanotubes exist; but they can be divided in two main categories: singlewalled (SWNT) and multi-walled (MWNT). The form of nanotubes is identified by a sequence of two numbers, the first one of which represents the number of carbon atoms around the tube, while the second identifies an offset of where the nanotube wraps around to.

Synthesis by Chemical Vapor Deposition

Multiwall carbon nanotubes have been grown by catalytic chemical vapour deposition using iron catalyst particles drop cast onto etched silicon wafers. The catalyst used was poly(styrene-vinylferrocene) in toluene solution which has an iron content of 2.1%. The etched silicon wafers have trench regions of varying widths ranging from 0.32 to 1 m. For trench widths below 0.5 m the number of interconnecting tubes growing from one side of the trench to the other increases sharply. A significant proportion of these interconnects are found to be Y-junction and multiple junction MWNTs. A systematic study of the effects of each of the growth conditions (temperature, run time, gas flow, catalyst concentration and trench width) versus interconnect yield was carried out. Densities of ~ 1.6 interconnects per micron of trench are obtained, with junction structures accounting for 38% of these interconnects. Densities can be controlled through modification of chemical vapour deposition conditions.

Carbon nanotubes have been shown to possess a number of remarkable properties. It has previously been shown that carbon nanotubes can be grown by Chemical Vapour Deposition (CVD) in such a way as to span gaps between catalyst particles. The growth of junction nanotubes offers many exciting possibilities for electrical device applications including the introduction of carbon nanotubes into integrated circuit chip design. Though many of these applications require the use of single wall nanotubes (SWNT) the study of MWNT junctions is still useful both for applications directly requiring MWNTs for their metallic electrical behaviour such as interconnects and as a precursor for SWNT research. Though junction structure nanotubes have been made by other methods CVD allows in situ patterning of these structures Here we present a simple method of growing controllable densities of interconnect type MWNTs with high proportions of Y-junction and multiple junction nanotubes across etched patterns, using a simple catalyst preparation.(reference 1,2)

Fig .1 Schematic: Mulitwall Carbon Nanotubes: Synthesis The MWNTs were grown in a custom built CVD system based on a single-stage Linberg blue mini-mite horizontal tube furnace fitted with an 18mm inner diameter alumina furnace tube. The active gas used was acetylene, C2H2, with flow rates between 0.05 1 slm used, argon was used as the carrier gas with a flow ratio of 10:1 Ar: C2H2. Both gas flow rates were controlled using mass flow controllers. The active gas was flowed through the system in the temperature regime of 700 900C for between 40 120 minutes. The temperature was kept stable while the active gas was flowing. The substrates used were 10mm * 10mm Si/SiO2 wafer segments with a test card array of patterns etched into the surface. Each test segment used was selected to have at least one etched pattern of interest with each pattern covering an area of approximately 100 m2. The patterns used were all trench structures with widths ranging from 200 1000 nm, trench separations were of the order of 200 500 nm and trench depths of 300 400 nm. The catalyst used was a solution of a block co-polymer polystyrene-polyvinylferrocene (PS-PVP) in toluene that was simply drop-cast onto the substrate surface and the solvent allowed to evaporate off at room temperature. The PS-PVP was anionically synthesized in house(19), and characterized by Nuclear Magnetic Resonance and Gel Permeation Chromatography (not shown) to determine its iron content (2.1%).

Application
Conductive Plastics Much of the history of plastics over the last half century has been as a replacement for metal. For structural applications, plastics have made tremendous headway, but not where electrical conductivity is required, plastics being famously good electrical insulators. This deficiency is overcome by loading plastics up with conductive fillers, such as carbon black and graphite fibres (the larger ones used to make golf clubs and tennis racquets). The loading required to provide the necessary conductivity is typically high, however, resulting in heavy parts, and more importantly, plastic parts whose structural properties are highly degraded. Structural Composites The world-record properties of buckytubes are not limited to electrical and thermal conductivities, but also include mechanical properties, such as stiffness, toughness, and strength. These properties lead to a wealth of applications exploiting them, including advanced composites requiring high values in one or more of these properties. Molecular Electronics The idea of building electronic circuits out of the essential building blocks of materials molecules - has seen a revival the past five years, and is a key component of nanotechnology. In any electronic circuit, but particularly as dimensions shrink to the nanoscale, the interconnections between switches and other active devices become increasingly important. Their geometry, electrical conductivity, and ability to be precisely derived, make buckytubes the ideal candidates for the connections in molecular electronics. In addition, they have been demonstrated as switches themselves. Biomedical Applications The exploration of buckytubes in biomedical applications is just underway, but has significant potential. Cells have been shown to grow on buckytubes, so they appear to have no toxic effect. The cells also do not adhere to the buckytubes, potentially giving rise to applications such as coatings for prosthetics and anti-fouling coatings for ships. The ability to chemically modify the sidewalls of buckytubes also leads to biomedical applications such as vascular stents, and neuron growth and regeneration.

References
1 R. Andrews, D. Jacques, D. Quan, and T. Rantell. Multiwall Carbon Nanotubes: Synthesis and Application. Accounts of Chemical Research. Vol. 35, No. 12, 2002 2 Chemical Vapor Deposition 3 A Carbon Nanotube Page 4 Physical Properties of Carbon Nanotubes. 5 S.R.C. Vivekchand, L.M. Cele, F.L. Deepak, A.R. Raju, and A. Govindaraj. Carbon nanotubes by nebulized spray pyrolysis. Chemical Physics Letters. 386 (2004) 313-318