CHAPTER ‘THE CARBON ELEMENT AND ITS VARIOUS FORMS LL INTRODUCTION ‘The sixth in the periodic table of elements is the most significant element among the others on earth and an essential one for lie on it. The extraordinary ity of the chemical element carbon is to combine with itself and other chemical elements in different ways. Within the last 20 years, the research on new carbon materials is virtually explosive, Starting ftom the discovery of the fullerenes, a completely new field of research has opened up among materials science, physics, and chemistry, which deals exclusively with this single, built fasina 1g element, its properties and applications. ‘The inteoduetion chapter briefS about the element carbon and its classical allotropes like graphite and diamond. This chapter also contains a brief about fullerenes, CNTS, graphene, carbon nanoparticles and carbon nanosheets etc, 1.1.1 The element carbon Elemental carbon in different shapes played a role in human life long before the term “element” was even coined. The word “earbon” is derived from the Latin ‘word “carbo”, which to the Romans meant charcoal (or ember). Charcoal and soot have been known and utilized for various purposes since ~ 5000 BC. They were mainly obtained from wood and employed, for example, for metallurgic processes such as the production of iron. The first application of graphite is documented from the late central European Iron Age. It was excavated near Passau (Bavaria) and ‘employed to blacken pottery. The term “graphite” reflects its use as a pigment: derived from the Greek word “graphein”, which means to write. Pencils, thatbecame fashionable in the Middle Ages, originally were made from graphite, and ancient Egyptian papyri bear hieroglyphs written with ink were made from soot. Diamond, whose name isderived fom the Greek words “ Natural graphite for lubricants and shoe polish > Carbon black reinforcement essential to every automobile tre(Carbon black and lamp black found in all printing inks ‘Acetylene black in conductive rubber ‘Vegetable and bone chars to decolorize and purify sugar and other food vvy ‘Activated charcoal for gas purification and catalytic support Carbon-carbon composites for aircraft brakes and space shuttle components High-strength carbon fibers for composite materials Very large graphite electrodes for metal processing ‘Carbon black for copying machines Graphite brushes and contacts for electrical machinery Diamond optical window for spacecrafts, Polycrystalline diamond coatings for cuting tools vVvvvyvvyyy Low-pressure processed diamond heat-sinks for ultrafast semiconductors 1.3 STRUCTURE AND BONDING OF THE CARBON ATOM ‘The atomic numberof carbon atom is 6. The carbon atom bears sx electrons out of which two are tightly bound and closed tothe nucleus, the remsining four as valence electrons, The cletronic configuration is 13%, 2s% 2p ‘This implies @ bivalence, which in fact only exists in a few structures carbenes). Inthe vast imsjority ofits compounds, carbon is tetravalent. The preferred tetra valence may be explained with the hybridization model. The energetic difference between 2s and 2p-onbitas is rather low compared to the energy released in chemical bonding ‘Therefore, its possible for the wave functions of these orbitals to mix and form four equivalent hybrid orbitals. These sp'-hybrid orbitals are directed towards the four comers of tetrahedron circumscribed to the carbon stom. In dition, the 2s- orbital may mix with a lower number 2p-orbital to form sp*- or sp-hybrid orbitals, respectively. Depending on the degree of hybridization, the resulting compound shows different structural features: sp, sp” and sp’ respectively [1].1.4 CARBON ALLOTROPES AND COMPOUNDS Carbon exists in many more polymorphs (allotropes) like graphite, diamond, fullerenes, and other less common forms; all exist with the same building block, the carbon atom, but the way the building blocks are put together in different physical forms is different. In other words, they have distinet molecular or erystaline forms, ‘The capability of an element to combine its atoms to form such allotropes is not ‘unique to carbon. Inthe fourth column of the periodic table, there are other elem- cents like silicon, germanium and tin, which also have that characteristic feature. ‘However, carbon is unique in the number and the variety of its allotropes, These allotropes of carbon can be classified into three major categories; 1.4.1 The sp! structures ‘These include graphite, the graphitic materials, amorphous carbon, and other carbon materials. In these structures, the valance electrons of the carbon atom can ‘occur to form the three-2sp* hybrid orbitals leaving to form one un-hybridized 2p orbital. The sp* orbitals are equivalent, coplanar and oriented at 120° to each other ‘and form o-bonds by overlapping with orbitals of neighboring atoms. The remaining p-orbital on each C atom forms a u-bond by overlapping with the p orbital from the neighboring C atom, 1.4.2 The sp* structures ‘The sp? structures include diamond and lonsdaleite (a form detected in meteorites). In these structures, there are four equivalent 2sp' hybrid orbitals that are tetrahedrally oriented about the carbon atom and can form four equivalent {tetrahedral o-bonds by overlapping with orbitals of other atoms.1.4.3 The sp structures ‘The sp orbital (known as a diagonal orbital) is a merger of an s and ap orbital, which consists of two lobes, one large and one small. A sp bond consists of ‘vo sp orbitals, which, because of mutual repulsion, forms an angle of 180°, and, consequently, the sp molecule becomes linear, The bond, like all overlap bonds, is a sigma (@) bond and has high strength, The sp orbitals account for two of the electrons of the carbon atom. The other two valence electrons are free, delocalized pi-orbital electrons which are available to form subsidiary n-bonds in a manner similar tothe sp* hybridization, 1.4.4 The fullerenes ‘The fullerenes are considered to be another major allotropic form of earbon ‘that com nes both sp’and sp* bonds [7]. These allotropes are sometimes found in. combination such as some diamond-like carbon (DLC) materials produced by low- pressure synthesis, which are actually mixtures of microcrystalline diamond and graphite. DLC is composed of small crystallites which have a local atomic configuration that can be either tetrahedral (sp") or planar threefold (sp") but are small enough that electron diffraction patterns indicate an amorphous material. DLC has no long-range order but forms a random stable network, as a result, DLC is generally considered to be amorphous. It has also been clearly demonstrated that the physical and chemical properties of the DLC films are closely related to the ‘chemical bonding and the microstructure [8]. ‘Anyway, the properties of the various carbon allotropes ean vary widely. For instance, diamond is by far the hardest-known material, while graphite can be one of the softest. Diamond is transparent tothe visible spectrum, while graphite is ‘opaque; diamond is an eleetical insulator, while graphite is a conductor, and the fullerenes are different from either one. Yet, these materials are made of the same carbon atoms; the disparity is the result of different arrangements of their atomicstructure, Just as carbon unites easily with itself to form polymorphs, it can also, combine with hydrogen and other elements (0 give rise to an extraordinary number of compounds and isomers (ie., compounds with the same composition but ‘with different structures), ‘The compounds of earbon and hydrogen and their derivatives form the extremely large and complex branch of chemistry known as organic chemistry More than half-e-miliion organic compounds are identified and new ones are continuously discovered, In fact, far more carbon compounds exist than the compounds of all the other elements put together [9]. While organic chemistry is ‘not a subject ofthis work, it cannot be overlooked. 1.5 THE STRUCTURE OF GRAPHITE 1.8.1 General considerations and terminology ‘As a well-established allosrope of carbon, graphite is outstanding for the large variety of materials that can be produced fom its basic form such as extremely strong. fibers, easily sheared lubricants, gas-tight barriers, and gas audsorbers. The graphite erystal was an easly subject for application of X-ray iffcction [10], The common characteristic in all these diverse material is that they are all built upon the trigonal sp-bonding of carbon atoms. Strictly speaking, the term “graphite” by itself describes an ideal material with a perfect graphite structure and no defects whatsoever However, itis also used commonly, though incorrectly, to deseribe graphitic materials, These materials are either “graphitic carbons”, that i, the materials consisting of carbon with the graphite structure, but with a number of structural defects, or “non-araphitic carbons”, that is the materials consisting ofearbon atoms with the planar hexagonal networks of the graphite structure, but lacking the crystallographic order in the eirection [11]. This isa fundamental difference andthese two groups of materials are distinct in many respects, with distinet properties and different applications. 1.5.2 Structure of the graphite crystal ‘The basis of the crystal structure of graphite is the graphene plane; it is composed ofa series of such stacked parallel layer planes shown schematically in figure 1.1 (a), with the trigonal sp bonding. In figure 1.1 (a), the circles showing the position of the carbon atoms do not represent the actual size of the atom, However, each atom, in fact, contacts its neighbors. The carbon atom is bonded to three others, forming a series of continuous hexagons within each plane and it ean be called as an essentially infinite two-dimensional molecule. The bond is covalent (6) and has a short length (0.141 nm) and high strength (524 kJ/mole). The un- hybridized fourth valence electron is paired with another delocalized electron of the adjacent plane by a much weaker Vander Waals bond (a secondary bond arising from structural polarization) of only 7 ki/mol(n). Heragonal Unt Cell Rhomabehedkal Stacking Fig. 1.1 () and (b) Crystal structure of graphite showing-ABAB-stacking sequence (Hexagonal) and Rhombohedral stacking respectively.Carbon is the only element to have this particular layered hexagonal structure. The spacing between the layer planes is relatively large (0.335 nm) or ‘more than twice the spacing between atoms within the basal plane and approximately twice the Vander Waals radius of carbon. The stacking of these layer planes occurs in two slightly different ways: hexagonal and rhombohedral 1.8.2.1 Hexagonal graphite ‘The most common stacking sequence of the graphite crystal is hexagonal with s-ABABAB-stacking order as shown in figure 1.1(a). The exact cexystallographie description of this allotropic form is given by the space group 670.8 pm). Hexagonal graphite is thermodynamically stable approximately up to 2600 K and 6 GPa, Atoms of the alpha (a) type, which have neighbor atoms in the adjacent planes direetly above and below, are shown with closed circles. Atoms of the beta (B) type, with no corresponding atoms in these planes, are shown with open circles. ‘sy -P6,/mme (unit cell constants: a= 45.6 pm, 1.5.2.2 Rhombohedral graphite ‘The other graphite structure is rhombohedral with the stacking order- ABCABCABC-(as shown in figure 1.1 (b)). The earbon atoms in every third layer are superimposed. The erystallographic description is given by the space group D's = Rm, The etystal lattice parameters are ay ~ 0.2256:nm and co ~ 1.006 nm. The proportion of rhombohedral graphite can be increased substantially by deformation process, such as grinding [12]. Whereas it reduced by high temperature heat treatment, showing that the hexagonal form is more stable, because it is thermodynamically unstable and can be considered as an extended stacking fault of hexagonal graphite, Itis never found in the pure form, but always in a combination with hexagonal graphite, at times up t0 40% in some natural and synthetic materials. It usually reverts to the hexagonal form during heat treatment above1300 °C. It should be noted that in both structures, hexagonal and rhombohedral, no basal plane lies directly over another. 1,53 The various polyerystalline forms of graphite ‘The ideal hexagonal graphite structure described above is composed of theoretically infinite basal planes with perfect -ABAB- stacking, with no defects Whatsoever. Such an ideal structure is, of course, never found, either in natural or synthetic graphite 1.5.3.1 Polycrystalline graphite Graphite materials, such as pyrolytic graphite, carbon-fiber-carbon matrix composites (carbon-carbon), vitreous carbon, carbon black, and many others, are actully aggregates of graphite erystalites, in other words, polyerytalline graphites 13}, These crystallites may vary considerably in size. For stanee, the apparent tayslallite size perpendicular to the layer planes (L.) of some vitreous easbons may be as small as 1.2 nm, which is the length of a few atoms, or up to 100 nm found in highly ordered pyrolytic graphites. The layer planes may or may not be perfectly patallel to each other, depending whether the material is graphitic or non-graphitie carbon, The aggregates of crystallites also have widely different sizes and properties. ‘Some, such as soot, are extremely small and contain only a few small erystallites. In such cases, the properties are mostly related (o the surface area, Other ageregates may be relatively large and free of defects and essentially parallel to each other, in which ease the structure and its properties closely match those of the ideal graphite crystal. Such large aggregates are often found in pyrolytic graphite, In other aggregates, the erystallites have an essentially randomorientation. This occurs in turbostratic or amorphous. In such cases, the bulk properties are essentially isotropic. 1.6 DIAMOND Diamond is an important commodity as a gemstone and as an industrial ‘material and there are several excellent monographs on the science and technology of this material (6, 14, 15] 1.6.1 The erystal structures of diamond Diamon« ‘a relatively simple substance in the sense that its structure and properties are essentially isotropic, in contrast to the pronounced anisotropy of ‘graphite. However, unlike graphite, it has several crystalline forms and poly types. 1.6.1.1 Cubie and hexagonal diamond Bach diamond tetrahedron combines with four other tetrahedral to form strongly bonded, three-di structures, wensional and entirely covalent crystal Diamond has two such structures, one with a cubic symmetry (the more common and stable) and one with a hexagonal symmetry found in nature as the mineral Tonsdaleite. 6.1.2 Cubie structure of the diamond Diamond is most frequently found in a cubie form in which each tetrahedron of the hybridized carbon atom combines with four other hybridized atoms to form a three-dimensional, entirely covalent, lattice structure with equal angles to each other of 109° 28!, the C-C bond length is 154 pm. shown schematically in figure 1.2. From the geometrical standpoint, the carbon nucleus can be considered as the centerof a cube with each of the four orbitals pointing to four altemating comers of the cube. Fig. 1.2 Three-dimensional representation of sp’ covalent bonding (diamond structure). 1.6.1.3 Hexagonal structure of the diamond Hexagonal diamond (Lonsdaleite) is extremely rare in nature. Tt was first discovered in a meteorite from Arizona in 1967. Still it is possible to obtain Lonsdaleite from graphite by exposing the latter to extreme pressure along the 7= axis at ambient temperature, The hexagonal lattice (Wurtzite type) like its cubic relative is built from tetrahedrons of carbon with a C-C bond length of 152 pm but these are arranged in a different way (figure 1.3) [7]. The unit eell contains four ‘toms, and the lattice parameters are ay = 252 pm and cy 412 pm.Fig. 13 The lattice structure of hexagonal diamond. The arrangement of atoms in the horizontal erystal plane somewhat resembles “wavy” graphite structure. Diamond is scarce and costly and this has motivated researchers, in the last fone hundred years or $0, to try to duplicate nature and synthesize it. These efforts are finally suceceding and the scarcity and high cost are now being challenged by the large-scale production of synthetic diamond. The properties of these synthetic diamonds are similar (and in some cases superior) to those of natural diamonds at a ‘cost which may eventually be considerably lower. 1.6.2 The four categories of synthetic diamond Modern diamonds belong to one of the four distinct categories: 1. Natural diamond, stil essentially the only source of gemstones and by far the leader in terms of monetary value. 2. High-pressure synthetic diamond, taking an increasing share of the industrial ‘market, particulary in wear and abrasive applications. 3. CVD (vapor-phase) diamond, potentially important but still basically atthe Inboratory stage with few applications in production 4. Diamond-ike carbon (DLC), also recent but with growing applications in opties and other areas1.6.3 Properties of diamond Diamond has outstanding properties, summarized as follows: ¥ thas the highest thermal conductivity of any solid at room temperature and iis five times that of copper. > It is the ideal optical material capable of transmitting light from the far- infrared to the ultraviolet. > Tthas an unusually high index of refraction. > lis semiconductor properties are remarkable, with fifteen times the average electric breakdown of common semiconductors, five times their average hole mobility and a dielectric constant that is half ofthat of silicon ILis extremely resistant to neutron radiation. Itis by far the hardest-known material thas excellent natural lubricity in ar, similar to that of Teflon, thas extremely high strength and rigidity. vvyvvy Ichas the highest atom-number density of any materi 1.7 THE STRUCTURE OF THE FULLERENE MOLECULES 1.7.1 General considerations ‘The discovery of lrg, sold carbon molecules wilh great stability are the so- ty of carbon molecules known to exist and is opening an entirely new chapter on the called “fullerenes”, which has considerably extended the scope and vari physics and chemistry of carbon with many potential applications. The fullerenes can be considered as another major allotrope of carbon and its frst stable, finite and diserete molecular form, In that respect, they are different from the other two allotropes graphite and diamond, which are not molecular but are infinite- network solids, The fullerene molecule is the fundamental building block of the crystalline phase, by doping and chemical reactions, it forms the basis of a large family of materials many of those having especially interesting properties.Existence of a stable molecule or cluster with 60 carbon atoms (designated Cig) was established experimentally by Kroto and Smaelly while performing the mass spectrographic analysis of carbon vapor in 1985. In addition, they also observed the presence of even-numbered clusters of earbon atoms in the molecular range of Cyy~ Cyw [16-18]. These scientists have given the name of “fullerene” to this family of closed cage carbon molecules because of their resemblance to the geodesic domes designed and built by R. Buckminister Fuller [19}. The practical synthesis of fllerenes as solid ageregates was demonstra- ted by Kratschmer and Huffinan in 1990 by the simple evaporation of a graphite electrode [20]. 1.7.2 Molecular structure of the fullerenes 2.1 Geodesic structure Unlike graphite or diamond, the fullerenes are not a single material, but a family of molecular, geodesie structures in the form of cage-like spheroids. They are built up of a network of five-membered rings (pentagons) and six-membered rings (hexagons). In order to close into a spheroid, these geodesic structures must have exactly twelve pentagons, but can have a variable number of hexagons (m), with the general composition: C3yraq, Such an even-numbered distril unique to the element carbon 1.7.22 Atomie bonding In order to account for the bonding of the carbon atoms of a fullerene molecule, the hybridization must be a modificati diamond and sp" hybridization of graphite, It is in such a way that the sigma (0) orbitals no longer contain all of the s-orbital character and the pi (a) orbitals are no of the sp? hybridization of longer of the purely p-orbital character as they are in graphite. Unlike the sp* or sp? hybridizations, the fullerene hybridization is not fixed, but has variablecharacteristics depending on the number of carbon atoms in the molecule. This ‘number varies from twenty for the smallest geometrically feasible fullerene Cay to infinity for graphite (which could be considered as the extreme case of all the possible fullerene structures), 1.7.3 The fullerene family ‘Theoretically, many fullerene structures are possible, some with hundreds of atoms. Out of those, five have been unambiguously identified and structurally characterized so far, they are Cig, Cro, Crs Crp and Cee [21], 1.74 Related structures ‘The spheroid fullerenes such as Ca are not only a type of large curved carbon molecules appeared. Geometrically many such structures are feasible [22]. Ijima and his co-workers have actually detected carbon molecular structures by the formu of eylindsical tubes, eased ‘uansinission election microscopies Usat an by polyhedral caps and known as “buckytubes' arranged in a helix around the tube axis and some have a negative curvature [23] ‘These structures have the hexagons ‘The defect in the hexagonal network that triggers the formation of such structures is believed to be a single heptagonal ring. Some of these tubes are whisker-like and ‘may reach micron size. 1.8 GRAPHENE, Graphene is an extended two-dimensional (2D) sheet of carbon atoms bound by the nearest strong neighbor sp? bonds and ordered in the form of a 2D honeycomb lattice. The carbon-carbon bond length in graphene is about 0.142 nm [24]. Graphene sheets stack to form graphite with an inter planar spacing of 0.335, fam, Within one graphene layer, the carbon atoms are situated at the comers of regular hexagons that constitute a wo dimensional fattice. From each C-atom, there‘are three o-bonds leading along the hexagons'edges, which correspond to sp hybridization, andonly three out of four valence electrons participate in hybridization. The remaining electrons contained in the peorbitals are also interacting and form a w-cloud that is delocalized over the entire graphene layer. ‘The electrons, thus, behave like a two dimensional electron gas, and by their ‘mobility, they cause material properties like an anisotropic electrical conductivity ‘An extremely well studied form of carbon has historically attracted attention because of its unique electronic and structural properties. Subsequent work has revealed a class of remarkable quantum electronic transport phenomena in ultrathin, one and few layer. samples [25-27]. Indeed many of the unusual electronic phenomena observed in graphene arise from a particular topological property ofits low-energy spectrum. The graphene “‘nonbonding’* n electrons form its valence and conduction bands [28, 29], and these bands meet at discrete critical points atthe ‘comers (conventionally labeled K and K') of its 2D Brillouin zone, The energy bands sperse linearly away from the touching, points. This peculiar topological behavior is responsible for many of the interesting electronic effects observed at low energy. Grapahene is the basic structural element of some of carbon allotropes including graphite, charcoal, carbon nanotube and fullerenes. It can also be considered as an indefinitely large aromatic molecule and the limiting case of the family of flat polycyelic aromatic hydrocarbons. 1.9 CARBON NANOTUBES. CNTs are one of the eminent allotropes of carbon with a cylindrical nanostructure. These fascinating objects represent another modification of the ‘element carbon. A sheet of paper is rolled up with its edges connected in a butt joint to generate a tube, Performing this experiment hypothetically with a graphene layer results in a carbon tube. These structures are entirely made up from carbon atoms ‘and accommodate a cylindrical cavity. Several of these tubes may fit one intoanother (o make a MWNT. The diameter of both, SWNT and MWNT species can ‘be measured on the nanometer scale and so they have been named as CNTS. Inhis pioneering work, Bacon in 1960, synthesized graphite whiskers, which he described as serolls, uses essentially the same conditions as for the synthesis of CNTs [30]. These are long cylinders of 3-coordinated carbon, slightly pyramidalized by curvature [31] from the pure sp? hybridization of graphene, toward the diamond-like sp*, Infinitely long in principle, a perfect tube is capped at both ends by hemi-fullerenes, leaving no dangling bonds. These cylindrical carbon molecules have unusual properties, which are valuable for nanotechnology, clectronies, optics and other fields of material science and nanotechnology. Their derived from their long, hollow structure with the walls formed by one- nam atom thick sheets of carbon, called graphene. These sheets are rolled at specific and discrete (“chiral”) angles, and the combination of the rolling angle and radius decided the nanotube properties. 1.9.1 Single walled carbon nanotubes ‘An SWNT can be envisioned as a narrow rectangular strip of nanoscale ‘graphene “chicken wire” with carbon atoms are separated by 0.14 nm apart at each apex, rolled up into a seamless eyfinder of 1 ~10 nm in diameter and as long as several micrometers. “graphene” refers to a monolayer of sp’-bonded carbon atoms. ‘The way the graphene sheet is wrapped is represented by a pair of indices (n, m). The integers “un” and “m’ denotes the number unit vectors along the two directions in the honey comb erystal lattice of graphene, [fm =0, the nanotubes are called zig~ ag, nanotubes, and if them correspond to high symmetry SWNT; in zig-zag tubes, some of the C-C bonds lie parallel to the tube axis, while in “armchair” tubes, some bonds are perpendicular to the axis. Otherwise, they are called the chiral. SWNTS are an 'm the nanotubes are called armchair nanotubes. Two of important variety of CNTs because most of their properties change significantly with the (n,m) values, and this dependence is non-monotonic. In particular,their band gap can vary from zero to about 2 eV and their electrical conductivity ean show metallic or semiconducting behavior [32] 1.9.2 Multi walled carbon nanotubes MWNTs consist of multiple rolled layers (concentric tubes) of graphite. ‘Tere are two models that can be used to describe the structures of MWNTS. In the “Russian dl!" model, sheets of graphite are arangein concent elinders. In the “Parchment mode" single sheet of graphite is rolled in round isl resembling a scroll of parchment or a rolled newspaper. The interlayer distance in MWNTs is close to the distance between graphene layer in araphite, whichis approximately 34 A. Muli-wall tubes have two advantages over ther single-wall cousins. The rmultéshll structure is stiffer than the single-wall one, especially in compression. Large-scale syntheses by enhanced Chemical Vapor Deposition (CVD) processes are many, while for sinleavall thes, only the Rice HiPeo process appears 0 be sealable, Mul-vall tutus are intrinsically usted since i is impossible to sat eptaxy simultancously, oF compatbiliy of wrapping indices (0, m) on jcent sell, wih a very strong tendency to malntin the ltr shell spacing close to that of the sraphite interlayer spacing of 3.38 A. Experimentally, the inter-shell in which thee ABAB:stackng ode is severly disrupted [33]. CNTs are the strongest and stfest materials yet discovered in terms of tensile strength and elastic modulus correlations in MWNTs are characteristic of turbo stratic graphi respectively. This strength results from the covalent sp bonds formed between the individual carbon atoms, In 2000, a MWNT was tested to have a tensile strength of 63 GPa [34), 1.10 CARBON NANOPARTICLES In addition to diamond and amorphous films, nonstructural forms of carbon may, also, be formed from the vapor phase. Here, stabilization is achieved by the formation of closed shell structures that obviate the need for surface heteroatom tostabilize dangling bonds, as is the case for bulk crystals of diamond and graphite. The classical example of closed-shell stabilization of carbon nanostructures is the formation of Cw molecule and other fullerenes by electric are evaporation of zaphite [35] Soot like activated carbon also comes under this category because of its high specific surface due to is particle structure, The small and ieregularly arranged grap domains cause the material to be practically isotropic. Soot ean bbe made starting from natural gas, methane or acetylene, the latter yielding acetylene black with its particularly high content of carbon (98% - 100%). 1.11 DIFFERENT METHODS OF SYNTHESIS ‘This section deals with different methods of synthesis of carbon nanostructures. It also discusses about the failure of the previously discussed ‘methods and the favorability of plasma systems in the growth of carbon ‘nanostructures at low temperatures. It also presents in brief, points about the RF- PECVD by which the synthesis of carbon nanostructures has been cartied out ‘throughout this research work. This section also briefs about the importance of variation parameters in controlling the carbon nanostruetures diameter, length and growth site and formation density. 1.11.1 Laser ablation In 1995, Smalley's group [36] at Rice University reported the synthesis of CNTs by laser vaporization. This technique, as well, has been used for the generation of fullerene clusters. The laser vaporization apparatus used by Smalley's inuous (39, 40] laser is used to vaporize a graphite target in an oven at 1200 °C, The main difference between continuous and pulsed laser is that the pulsed laser demands a much higher light intensity (100 kW/em? compared with 12 kW/em’).. group is shown in figure 1.4, A pulsed [37, 38}, or cora tie Fig. 14 Schematic drawing ofa laser ablation apparatus, ‘The oven is filled with helium or argon ga in order o keep the pressure at 500 Tor [41]. A very hot vapor plume forms, then expands and cools rapidly by an efficient cooling device (usually cooling finger made of copper) situated at one end to collect the nanotubes. As the vaporized species cool, small carbon molecules and atoms quickly condense to form lager chistes, possibly inching fullerenes. The catalysts also begin to condense, but more slowly a ist, and then attach to carbon clusters and prevent their closing into cage structures. Catalysts may even open cage structures when they attach to them, From these initial clusters, tubular molecules grow into SWNTs until the catalyst particles become foo large, Fallerens are also produced by laser ablation of catalystfled graphite, as is the case when no catalysts are included in the target. However, subsequent laser pulses excite fullerenes to emit C3 that adsorbs on catalyst particles and feeds SWNT growth (42, L112 Are discharge ‘The method developed by Kratschmer and co-workers for the preparation of ‘macroscopic amounts of fullerenes can also be adapted to produce nanotubes. The ‘method was initially used for producing Cyy fullerenes. Perhaps it has also beenn ‘employed to make MWNTS, but now SWNTs production has succeeded with this method as well. However, a technique produces @ mixture of components and requires separating nanotubes from the soot and the catalytic metals present in the ‘nude product (41) The essential differences of an are discharge apparatus for nanotube preparation are in increased pressure of an inert gas and the distance between the lectrodes contrary to fullerene production, there must be under no circumstances touch cach other. CNTs are created in this method through arc vaporization of two carbon rods placed end to end, separated by approximately Imm in an enclosure that is usually filled with inert gases like helium or argon at low pressure in between 50 and 700 mbar. A direct current of $0 10100 A driven by approximately 20 V creates a high temperature discharge between the two electrodes. Earlier investigations have shown that it is also possible to create nanotubes with the are method in liquid nitrogen [43] ‘ate dischagge method. sure 1.5 represents the experimental set up for an gaa Cathode Inert Gas Deposition Anode Fig, 15 Experimental set-up for an are discharge.Producing nanotubes in high yield depends on the uniformity of the plasma are and the temperature of the deposit formed on the carbon electrode. Temperature of carbon, and metal catalyst densities affect the diameter distribution of nanotubes, (aq). ‘A second possibly economical route to mass production of MWNTS is, synthesis by plasma rotating arc discharge technique [45]. The centrifugal force caused by the rotaion generates turbulence and accelerates the carbon vapor perpendicular tothe anode, In addition, the rotation distributes the micro discharges uniformly and generates stable plasma. Consequently, it increases the plasma volume and raises the plasma temperature, Figure 1.6 represents the schematic diagram of plasma rotating are discharge method sm | oe Fig. 1.6 Schematic diagram of plasma rotating electrode system. At a rotation, speed of S000 rpm a yield of 60 % was found at a formation temperature of 1025 °C without the use of a catalyst, The yield increases up to 90% after purification ifthe rotation speed is increased and the temperature is enlarged to 150°C,1.12 CHEMICAL VAPOR DEPOSITION Chemical Vapor Deposition (CVD) is a versatile process suitable forthe ‘manufacturing of coatings, powders, fibers, and monolithic components, With CVD, itis possible to produce most metals, many nonmetallic elements such as carbon and silicon as well as a large number of compounds including, carbides, nitrides, oxides, intermetallics, and many others. This technology is now an essential factor in the manufacture of semiconductors and other electronic components, in the coating of tools, bearings, and other wear resistant parts and in ‘many optical, optoelectronic and corrosion applications [46]. 1.12.1 Definition of CVD CVD may be defined as the deposition ofa solid on a heated surface from a ‘chemical reaction in the vapor phase. It belongs to the class of vapor-transfer processes, which is atomistic in nature that is the deposition species are atoms or molecules of a combination of these. 1.12.2 Historical perspective CVD is not a new process. As stated in the pioneer work of Powell, Oxley, and Blocher [47], ts first practical use was developed in the 1880s in the production of incandescent lamps to improve the strength of filaments by coating them with carbon or metal. In the same decade, the carbonyl process was developed by Ludwig Mond and others for the produ ‘were issued during that period covering the basis of CVD [48]. fon of pure nickel. A number of patents CVD can be classified by the method used to apply the energy necessary to activate the CVD reaction, e., temperature, photon, or plasma.1.12.3 Advantages and limitations of CVD CVD has several important advantages, which make it the preferred process in ‘many cases, These can be summarized as follows: > It is not restricted to a line-of-sight deposition, which is a general characteristic of sputtering, evaporation and other PVD processes, > ‘The deposition rate is high and thick coatings ean be readily obtained (in some cases centimeters thick) and the process is generally competitive and, in some cases, more economical than the PVD processes. > CVD equipment does not normally require ultrahigh vacuum and generally cean be adapted to many process variations. Its flexibility is such that it allows ‘many changes in composition during deposition and the co-deposition of clements or compounds readily achieved. 12-4 Thermal chemical vapor deposition In this method, Fe, Ni, Co o an alloy of the three catalytic metals is initially deposited on a substrate, After the substrate is etched in a diluted HF sol with, distilled water, the specimen is placed in a quartz boat, The boat is positioned in a CVD reaction furnace, and nanometer-sized cataly je metal particles are formed after an additional etching ofthe catalytic metal film using NH gas at a temperature of 750° to 1050 °C. As CNTs are grown on these fine catalytic metal particles in CVD synthesis, forming these fine catalytic metal particles is the most important process. Figure 1.7 shows a schematic diagram of thermal CVD apparatus in the synthesis of CNTs.26 Theme Cole etic = ro =) EBs - Tomperae 1 Heater PR Fig. 17 Schematic diagram of thermal CVD apparatus, When growing CNTS on a Fe catalytic film by thermal CVD, the diameter range of the CNTs depends on the thickness of the catalytic film, By using a thickness of 13 nm, the diameter distribution lies between 30 and 40 nm, When a thickness of 27 nm is used, the diameter range is between 100 and 200 nm. The NTs formed are multi-walled [49], 1.12.5 Failure of previous methods and the favorability of plasma systems in the growth of carbon nanostructures at low temperatures ‘The systems reviewed in the previous sections (1.11 and 1.12) for the growth of carbon nanostructures needs high temperatures. The needed temperatures are roughly about 1000 to 2000 °C and more than that. Direct Current (DC) is the general source of the temperature in the case of arc discharge, laser ablation and rotating ate discharge. Whereas, resistance heating, high frequency induction, radiant heating and hot plate heating, or any combination of these are the sources of thermal CVD. However, the carbon nanostructures produced by these methods are in use for applications like electronics, where the connections are highly temperatures sensitive. In addition, the carbon nanostructures produced by these ‘methods are co-existed as by products in the generation of CNT.Another main drawback of these systems is the growth of carbon nanostructures on the flat thin substrates like Si, Mgo, Cu, ete., also, they are failures in the growth of individual and positional carbon nanostructures on Si substrate particularly for applications in electronics 13 PLASMA CVD. ‘Thermal CVD, reviewed above, relies on thermal energy to activate the reaction, and deposition temperatures are usually high. Thermal CVD requires high temperature, generally from 800 to 2000 °C, which can be generated by resistance heating, high-frequency induction, radiant heating, hot plate heating, or any combination of these, In plasma CVD, also known as plasma-enhanced CVD (PECVD) or plasma assisted CVD (PACVD), the reaction is activated by plasma and the deposition temperature is substantially lower. Plasma CVD combines a chemical and a physical process and may be said to bridge the gap between CVD anxl PVD. I respect, is similar to PVD processes operating in a chemical environment, such as reactive sputtering, Plasma CVD was first developed in the 1960s for ide, The semiconductor applications, notably for the deposition of siticon nit ‘number and variety of applications have expanded greatly ever since and itis now a major process on par with thermal CVD. 1.13.1 Advantages of plasma CVD With plasma CVD, a deposit is obtained at temperatures where no reaction ‘whatsoever would take place in thermal CVD. ‘This is its major advantage since it permits the coating of low-temperature substrates, such as aluminum (which might ‘otherwise melt), organic polymers (which would otherwise degrade and outgas) or ‘of metals oF metal alloys which experience structural changes at high temperature, ‘such as austenitic steel. Dopants for semiconductors, such as boron and phosphorus,ccan also readily diffuse between buried layers of the device if the temperature exceeds 800 °C, resulting in detrimental changes in the semiconductor properties. Another advantage is that the effects of thermal expansion mismatch between substrate and coating and the resulting stresses are reduced since the temperature of deposition remains low. In addition, the deposition rates are usually increased and, since the pressure is low (in the case of glow-discharge plasma CVD), the rate controlling factor is surface kinetics Which leads to greater uniformity. The low temperature of deposition also favors the formation of amorphous or very fine-grained polycrystalline deposits, which often have superior properties. 1.14 PLASMA ENHANCED CHEMICAL VAPOR DEPOSITION SYSTEM PECVD is a process used to deposit thin films from 2 gas state to a solid state on a substrate, Chemical reactions are involved in the process, which occur after ercation of plasma of the reacting gases. The plasma is generally created by RF (AC) frequency or DC discharge between two electrodes, the space between which is filled with the reaction gases. Plasma is any gas in which significant percentage of the atoms or molecules are ionized. Fractional ionization in plasmas used for deposition and related materials processing varies from about 10 in typical capacitive discharges to as high as 5 — 10% in high-density inductive plasmas. A. simple Direct Current (DC) discharge can be readily created between two conductive electrodes, and made suitable for deposition of conductive materials. However, insulating films will quickly extinguish this discharge as they are deposited. Altematively, a discharge can be obtained by applying a Radio Frequency (RF) signal between two parallel electrodes. The RF powered PECVD system procured from HIND HIVAC, Bangalore is a PECVD system powered by a S00W RF power source, Pumped by a combination of rotary vane pump, roots booster pump and an oil diffusion pump, a pressure of about 1x10 mbar ean routinely be achieved in the system. Equipped with pirani gauges, a high-resolution2 digital pirani gauge and penning gauge for measuring vacuum, the system becomes 4 robust equipment capable of producing reliable rosulls. Feed gases (argon & ‘methane are pumped through appropriate mass flow controllers for perfect contol Featuring a substrate heater (800 °C), the system is ideal for fabrication of CNTs, DLC thin films and other carbon nanostructures. Figure 1.8 represents the photograph of RF-PECVD. Fig. 1.8 Photograph of RE-PECVD system. (Nanotechnology Research Centre, SRM University). Figure 1.9 shows the intemal view of the HIND HIVAC RF-PECVD. From this figure, one can see the view connestions of roughing vale, backing vale and throttle vale with the roots, rotary and oil diffusion pump uses at different stages of ‘chemical reaction to acquire high vacuum roughly about 10-6 mbar.Fig. 1.9 Block diagram of the RF-PECVD. ‘One can also view the three different pirani gauges PRI, PR2 and PR3 are connected to backing vale, roughing valve and high vacuum vale to observe the ‘vacuum at each and every stage of reaction 1.14.1 Importance of variation of parameters After the introduction of CNTS in to the field of material science a great deat of researches have been devoted to CNTs and different types of carbon nanostructures like sheets, particles, rods, et, Particularly, carbon nanostructures of different shapes are capable of biting extraordinary electrical, thermal and! mechanical properties. For example inthe case of applications like field emitter in field emission displays, well-aligned CNTs having high aspect ratio are required. For the applications of the tips in the Scanning Probe Microscope (SPM), CNTs with a small diameter and high mechanical strength are required. Furthermore, individual grown carbon nanostructures on Si substrates are expected tobe useful in nano-electronies.In order to utilize such prominent characteristics in wide application fields, hhowever, it is inevitable to control carbon nanostructures diameter, length and ‘growth site and formation density All the above-mentioned physical dimensions of nanostructures grown on the substrates are controlled by varying different parameters like electric field, temperature of deposition, pretreatment of catalyst and gas composition. ‘Therefore, to carry out these types of operations in the synthesis stage, PE~ ‘CVD has been designed with the arrangements of digitally varied parameters for the growth of the carbon nanostructures on different types of substrates depending upon different types of applications. 1.15 THESIS STRUCTURE ‘This thesis has dhe following stucture. Chupter 1 of dhe dhesis briefly discussed about the element of carbon and its classical allotropes like graphite and «diamond; it also explains briefly about the recently discovered allotropes of earbon like fullerenes, carbon nanosheets, CNTs and carbon nanoparticles. It also deals with different methods of synthesis of carbon nanostructures andthe failure of previously discussed methods in synthe synthesis temperatures. It also briefs the method, which is used to grow carbon nanostructures in the present work (RF-PECVD). This chapter also presents briefly ing carbon nanostructures at low bout the importance of the variation of parameters in controlling diameter, length, and growth site and formation density of carbon nanostructures on Si substrate. The characterization techniques used in this work to analyze the samples are briefly discussed in Chapter 2. For clarity, a literature review relevant to discussions in specific chapters has been included in the introductory sections as well as in the main text, of each chapter. In addition to this experimental and‘conclusion has been discussed in the respective chapters corresponding to the work presented. Chapter 3 presents the synthesis of carbon nanosheets and carbon nanoparticles by RF-PECVD. Chapter 4 deals with the synthesis of carbon nanostructures at possibly less temperature; it also describes the growth mode of the carbon nanostructures and the factors that influencing the growth at less synthesis temperature. Chapter 5 focuses on the magnetic behavior of carbon nanosheet like structures as function of time of deposition. Chapter 6 covers the effect of variation of parameters like temperature, time of deposition and gas composition on the ‘growth and morphology of carbon nanostructures, Chapter 7 provides the effect of pre-etching duration on the growth and morphology of carbon nanostructures. Chapter 8 presents the growth and characterization of branched CNTs on the Si substrate with and without SiO; layer. Chapter 9 carries summary and the future direction of the work.