CHAPTER 1 INTRODUCTION

1.1 BRIEF HISTORY OF GRAPHENE: The term graphene first appeared in 1987 [1] to describe single sheets of graphite as one of the constituents of graphite intercalation compounds (GICs);conceptually a GIC is a crystalline salt of the intercalate and graphene. The term was also used in early descriptions of carbon nanotubes [2], as well as for epitaxial graphene, and polycyclic aromatic hydrocarbons .Single layers of graphite were also observed by transmission electron microscopy within bulk materials in particular inside soot obtained by chemical exfoliation [3]. There have also been a number of efforts to make very thin films of graphite by mechanical exfoliation (starting from 1990 and continuing until after 2004) but nothing thinner than 50 to 100 layers was produced during these years. A key advance in the science of graphene came when Andre Geim and Kostya Novoselov at Manchester University managed to extract single-atomthick crystallites (graphene) from bulk graphite in 2004 [4]. The Manchester researchers pulled out graphene layers from graphite and transferred them onto thin SiO2 on a silicon wafer in a process sometimes called micromechanical cleavage [5] or, simply, the Scotch tape technique. The SiO2 electrically isolated the graphene, and was weakly interacting with the graphene, providing nearly charge-neutral graphene layers. The silicon beneath the SiO2 could be used as a "back gate" electrode to vary the charge density in the graphene layer over a wide range. Geim has received several awards for his pioneering research on graphene, including the 2007 Mott medal for the "discovery of a new class of materials free-standing two-dimensional crystals in particular graphene", the 2008 EuroPhysics Prize (together with Novoselov) "for discovering and isolating a single free-standing atomic layer of carbon (graphene) and elucidating its remarkable electronic properties", and the 2009 Korber Prize for "developing the first two-dimensional crystals made of carbon atoms". In 2008 and 2009, Reuters tipped him as one of the front-runners for a Nobel prize in Physics. On October 5, 2010, the Nobel Prize in Physics [6] for the year was awarded to Andre Geim and Konstantin Novoselov from the University of Manchester for their work on graphene.

1.2 WHY GRAPHENE: Switching to green technology is not only profitable but also ecologically beneficial. Green manufacturing and management is all about designing and producing products using eco-friendly green technologies and processes. This trend seems to be widening and we hear a lot of research in green technologies. Perhaps, some of these might get incorporated into products with a much improved efficiency and smaller foot print than current ones. One notable developement is the use of thin-film technology to make flexible and easy to handle mini, micro and nano scale devices. Now, just read about a significant breakthrough in Nano technology which will provide a good break for the electronics and similar technologies. We know, Graphite is widely used as a lubricant and as a moderator in nuclear reactors. Then, what about Graphene? Graphene is a new member of the of the two-dimensional (2-D) materials family, consists of a hexagonal array of bonded carbon atoms like those found in bulk graphite. Graphene is extremely different from most established three-dimensional (3-D) materials [7]. Besides, Intrinsic graphene is a semi-metal (zero-gap semiconductor).
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Today, many companies have started to make graphene and graphene oxide (GO) [8].Graphene Oxide is an insulating version of 'single atom thick' graphene, expected to find use in all kinds of material and electronic applications. By oxidising and then floating in water, the graphene flakes form a single sheet with very powerful carbon to carbon bonds [9]. Graphene Oxide is infact a natural insulator, but it is possible to modify it as a conductor (or semiconductor) by prodigious chemical processing. This nature-friendly, water-soluble product could find use in polymers,ceramics and metals,as thin films for electronics,as well as drug delivery devices [10]. This new material its very interesting due to its abnormal properties and characteristics. One of such Characteristics is its ability to remain stable in free state unlike other 2D materials known to be altered when being exposed to our environment. Another of graphenes interesting properties is its conductivity, which allows electrons to travel 100 times faster than in silicon which is higher than any other known material at room temperature. Besides these and other special and interesting characteristics Graphene has several potential applications. One of this potential uses for this material is as a sensor of gas molecules due to its two dimensional structure most of its matter would be in direct contact with the gas molecules making it more efficient in detecting these molecules [11]. Even though other materials have similar abilities when used in gas sensor, graphene is far more superior due to its electronic and conductive properties. Another of graphenes potential uses is in the field of integrated circuits due to graphenes ideal properties it could be fitted in to a field effect transistor making it more effective than and not as noisy as other material during use due to its high electron mobility. However this fascinating and groundbreaking material comes with a major draw back which is its inability to be mass produced. With out this major obstacle graphene could easily replace silicon as the main component for computer systems and other electronic.

CHAPTER 2 STRUCTURE OF GRAPHENE

Graphene is a two dimensional sheet of carbon atoms that are densely packed in a honeycomb crystal lattice structure. We can visualize graphite as many sheets of graphene stacked together [12].Lead of pencil is made of graphite, and when we write with it on a piece of paper, the graphite is cleaved into thin layers and make up the text or drawing that we are trying to make. Some of these thin layers will contain only a few layers or even a single layer of graphite, i.e. graphene [13].

Fig 2.1 : 3-D structure of Graphite made of layers of graphene stacked together

Fig 2.2 : 2D sheet of Graphene

Graphene sheets stack to form graphite with an interplanar spacing of about 0.335 nm, which means that a stack of 1mm/.335 nm=2.98 million sheets would be only one millimeter thick. It is the basic structural element of some of the carbon allotropes including graphite, charcoal, carbon nanotubes and fullerenes [14].Graphene is the basic structural element of some carbon allotropes including graphite, charcoal, carbon nanotubes and fullerenes. It can also be considered as an indefinitely largearomatic molecule, the limiting case of the family of flat polycyclic aromatic hydrocarbons [15]. Graphene is a 2D sheet of carbon atoms arrayed in a hexagonal honeycomb lattice. The sheet is held together with sp2 bonds between the carbon atoms separated by a distance of about 1.4 angstroms, making the sheet quite strong. A few such layers stacked on top of each other is still considered graphene; it takes at least 10 layers (and in some respects more like 100) before a sample becomes bulk graphite. There are about 3.4 angstroms between stacked sheets. The honeycomb lattice can be analyzed with a two-atom unit cell as a Bravais lattice. By mentally duplicating and translating this cell by a set amount along set translation vectors, the entire lattice can be constructed. There are two possible cuts along a honeycomb lattice; these are entitled \armchair" and \zig-zag" due to the appearance of the resulting jagged edge along such a cut. The orientation of a lattice, specically whether a cut or a current is along the armchair or zig-zag direction, has interesting fundamental effects on the electronic behavior of graphene [16].
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Fig 2.3: Lattice unit cell of graphene

Fig 2.4: armchair and zig-zag cuts along a graphene lattice.

CHAPTER 3 PROPERTIES OF GRAPHENE

Graphenes properties are remarkable which have evolved in many applications. Thinnest Imaginable material: Its height was measured to be just 0.33nm, almost one million times thinner than a human hair. Graphene is the ultimate 2-dimensional carbon molecule.

Fig 3.1: Graphene Easily available: Graphite, the well known 3-dimensional carbon allotrope found in our pencils, is nothing more than a stack of several graphene planes. Graphene shares its structure with two other materials which are exciting today's scientists: carbon nanotubes and fullerenes (also called bucky-balls), seen as a 1-dimension and 0dimension rolled pieces of graphene, respectively [17].

Although just one atom thick, graphene posses outstanding mechanical, electronic, optical, thermal and chemical properties, described below: Mechanical Properties: To calculate the strength of graphene, scientists used a technique called Atomic Force Microscopy. By pressing graphene that was lying on top of circular wells, they measured just how far you can push graphene with a small tip without breaking it.It was found that graphene is

harder than diamond and about 300 times harder than steel.

Fig 3.2: Graphene sheet illustrating mechanical properties

To put this into context, it will take the weight of an elephant balanced on a needle-point in order to break this one atom thick fabric! The tensile strength of graphene exceeds 1 TPa. Even though graphene is so robust, it is also very stretchable up to 20% of its initial length. It is expected that graphenes mechanical properties will find applications into making a new generation of super strong composite materials and along combined with its optical properties, making flexible displays [18]. Electronic Properties: Graphene is great conductor; electrons are able to flow through graphene more easily than through even copper. The electrons travel through the graphene sheet as if they carry no mass, as fast as just one hundredth that of the speed of light [19].

Fig 3.3: Graphene sheet Thermal Properties: Graphene is the perfect thermal conductor. Its thermal conductivity was measured recently at room temperature and it is much higher than the value observed in all the other carbon structures as carbon nanotubes, graphite and diamond (> 5000 W/m/K) [20].The study of thermal conductivity in graphene may have important implications in graphene-based electronic devices. As devices continue to shrink and circuit density increases, high thermal conductivity, which is essential for dissipating heat efficiently to keep electronics cool, plays an increasingly larger role in device reliability [21].
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 Optical Properties: Due to its unique electronic properties, it absorbs a high 2.3% of light that passes through it, which is enough that we can see it in air. To help enhance the visibility of graphene flakes we deposit them on to silicon wafers which have a thin surface layer of silicon dioxide [22]. Light shining on to these three-layer structures will be partially transmitted and partially reflected at each interface. This leads to complex optical interference effects such that, depending on the thickness of the silicon-dioxide layer (which we can control to a high degree of accuracy), some colours are enhanced and some are suppressed. This technique takes advantage of the same physics which causes the "rainbow effect" that you see when you have a thin layer of oil floating on water. In this case, the different colours correspond to longer/shorter optical path lengths that the light has had to travel through the oil film [23]. Chemical Properties: Graphene can absorb or reject different atoms and molecules. Single-layered graphene is more reactive than 2 or 3 layers, and its edges are more reactive than its surface. Unless its exposed to severe conditions, graphene is generally inert and wont react with most materials being exposed to it [24].

CHAPTER 4 GRAPHENE PRODUCTION

There are presently four main methods to produce graphene. They are tabulated below: Table 4.1: Brief Starting Material description of method Highly Ordered Repetitive Pyrolytic peeling highly Graphite(HOPG) ordered pyrolytic graphite Reduction of SiC silicon atoms at high temperature Graphene GO Oxide dispersion into hydrazine Gas Chemical mixtures(CH4 vapor and H2) deposition

Yield

Quality

Area

Low

Very High

Small

Low

Medium

Large (3-4 wafers)

High

Medium

Large

Very high

High

Very Large

4.1 MECHANICAL EXFOLIATION:

The top piece of tape is gently pulled apart from the bottom. Re-adhere the top piece to the bottom and pull apart again. Repeat this 4-5 more times with the same piece of tape. Throw away the top piece of tape. Get a fresh piece of tape, and repeat step 2. As we repeat this step, note that the bottom piece of tape is gradually covered with a shiny-gray graphite film. Repeat step 4, until the film is a dull gray. This will likely take 4-5 pieces of tape, depending on the initial amount of graphite. Next, adhere the sticky side of the bottom piece of tape to the shiny purple side of the silicon wafer piece. Press the tape firmly yet gently onto the wafer piece. The silicon wafer can now be viewed under an optical microscope with at least a 100X objective. The color and graphene thickness will vary depending on the microscope and thickness of the silicon dioxide, but Figure 1 represents an example sample. The wafer can also be viewed under an electron microscope or atomic force microscope if one is readily available [25].

Fig 4.1: Mechanically exfoliated graphene on SiO2 imaged with white light using an optical microscope 4.2 EPITAXIAL GROWTH: Graphene can also be obtained by heating silicon carbide to high temperatures which is typically greater than 1100 C to reduce it to graphene. Sample size produced is dependent upon the size of the SiC Epitaxial growth on silicon carbide. Epitaxy is a method of depositing a monocrystalline film on a monocrystalline substrate. Graphene can also be obtained by epitaxial growth on metal substrates like those of iridium, ruthenium etc. Graphene synthesized by chemical vapour deposition on thin nickel films yields high-quality sheets of few layer graphene of around 1 cm2. These sheets have already been tested for various electronic applications. A modified technique has been found in which copper foil is used where the growth automatically stops after a single graphene layer resulting in creation of large graphene films [26]. GRAPHENE

ON HEATING

SiC substrate

Fig 4.2: Growing Graphene on SiC

4.3 DECOMPOSITION OF GRAPHENE OXIDE(GO): Graphite oxide has attracted much interest recently as a possible route for the large-scale production and manipulation of graphene, a material with extraordinary electronic properties. Graphite oxide itself is an insulator, almost a semiconductor, with differential conductivity between 1 and 5103 S/cm at a bias voltage of 10 V. However, being hydrophilic, graphene oxide disperses readily in water, breaking up into macroscopic flakes, mostly one layer thick. Chemical reduction of these flakes would yield a suspension of graphene flakes. It was argued that the first experimental observation of graphene was reported by Hanns-Peter Boehm in 1962. In this early work the existence of monolayer reduced graphene oxide flakes was demonstrated [27]. The contribution of Boehm was recently acknowledged by Andre Geim, the Nobel Prize winner for graphene research. Partial reduction can be achieved by treating the suspended graphene oxide with hydrazine hydrate at 100 C for 24 hours, or by exposing graphene oxide to hydrogen plasma for a few seconds, or by exposure to a strong pulse of light, such as that of a Xenon flash. However, the conductivity of the graphene obtained by this route is below 10 S/cm, and the charge mobility is between 2 to 200 cm2/(Vs) for holes and 0.5 to 30 cm2/(Vs) for electrons. These values are much greater than the oxide's, but still a few orders of magnitude lower than those of pristine graphene. Inspection with the atomic force microscope shows that the oxygen bonds distort the carbon layer, creating a pronounced intrinsic roughness in the oxide layers which persists after reduction. These defects also show up in Raman spectra of graphene oxide. Additionally, exposing a film of graphite oxide to the laser of a Light Scribe DVD has also revealed to produce quality graphene at a low cost [28]. In this method, graphite is firstly oxidized to provide GO. By different exfoliation approaches, a single layer of GO, which is referred as graphene oxide was generated. Such graphene oxide can be reduced under various conditions to produce graphene in a large quantity. Graphene produced by this way has been given a variety of names, including: reduced graphene oxide (ReG), chemically-reduced graphene oxide (CRG), and graphene. For the sake of clarity, the product is here referred as reduced graphene oxide (ReG) though the distinction with pristine graphene will be made apparently. The two are often confused but the quality of graphene produced by graphite oxide reduction is much lower than e.g. scotch tape graphene due to incomplete removal of various functional groups. Even though simply reducing GO is not able to provide graphene with perfect structure, it offers incomparable advantages in large scale production of solution processable single graphene (or GO) layer with low cost. Therefore, extensive studies have been done to reveal the chemical structure of GO in aim to find out possible approaches to retrieve the honeycomb structure of graphene [29].

4.4 CHEMICAL VAPOUR DEPOSITION (CVD) METHOD: Graphene grown via chemical vapour deposition (CVD), a relatively new technique for producing large-area films of contiguous, multi-domain graphene. Once created, CVD graphene is transferable to diverse substrates, making the technique versatile for many applications. One such application is as an electrode in an organic solar cell. In CVD, a metal substrate such as copper is put into a furnace and heated under low vacuum to around 1000C. The heat anneals the copper, increasing its domain size. Methane and hydrogen gases are then owed through the furnace. The hydrogen catalyzes a reaction between methane and the surface of the metal substrate, causing carbon atoms from the methane to be deposited onto the surface of the metal through chemical adsorption . The furnace is quickly cooled to

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keep the deposited carbon layer from aggregating into bulk graphite, which crystallizes into a contiguous graphene layer on the surface of the metal [30].

Fig 4.4 : CVD growth on copper

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CHAPTER 5 APPLICATIONS OF GRAPHENE

5.1 GRAPHENE TRANSISTORS: A graphene transistor is a Nano scale device based on graphene, a component of graphite with electronic properties far superior to those of silicon. The device is a single-electron transistor, which means that a single electron passes through it at any one time [31]. A research team led by Professor Andre Geim of the Manchester Centre for Mesoscience and Nanotechnology built a graphene transistor and described it in the March 2007 issue of Nature magazine. Scientists have predicted that graphene transistors could scale to transistor channels as small as two nanometres (nm) with terahertz speeds. Before we go into the details of the working of Graphene based Transistors it is important for us to look into the electrical properties of Graphene which is base material of the transistor [32]. 5.1.1 GRAPHENES CHARGE CARRIERS ARE RELATIVISTIC: But why is there such interest in graphene? Aside from the obvious interest in the novelty of a two-dimensional crystal, graphene crystals exhibit unusual electrical properties that may prove useful both theoretically and practically. In particular, Graphenes charge carriers are very unusual in that they behave like mass less Dirac fermions and are most effectively described by the Dirac equation rather than the non-relativistic Schrdinger equation [33]: .........5.1 5.1.2 ANAMOLOUS QUANTUM HALL EFFECT IN GRAPHENE: In addition, graphene also exhibits an anomalous quantum hall effect. In classical electromagnetism, the Hall effect arises when a magnetic field is applied perpendicular to the surface of a solid carrying a current parallel to the surface. The Lorentz force causes positive and negative charges to build up on opposite sides of the solid, parallel to the current, producing a potential difference known as the Hall voltage. The direction the voltage points determines the charge of the charge carriers in the material. The quantum Hall effect (QHE) is identical to the classical Hall Effect except that the Hall voltage (and consequently the Hall resistivity and the Hall conductivity) occurs only in discrete steps equal to an integer times e2/h. In addition to the integer quantum Hall effect, there is another effect known as the fractional quantum Hall effect in which the Hall conductivity is equal to e2/h times a rational fraction that is less well understood. In the presence of a magnetic field, graphene produces yet another quantum Hall effect known as an anomalous quantum Hall effect. In the case of graphene, the Hall conductivity occurs in discrete integer steps like the conventional QHE, but is shifted by one-half of an integer as shown below in figure [34]. Graphene is an ideal system for examining the quantum Hall effect for a number of reasons. First, graphene samples are available in such purity that the charge carrier concentration can be tuned continuously from high concentrations of electrons to high concentrations of holes simply by changing the gate voltage. Second, the purity of the graphene samples is so high that the QHE can be observed even at room temperature, whereas most materials only exhibit the QHE at much lower temperatures. Finally, graphenes anomalous quantum Hall effect, by being shifted by half compared to most systems, exhibits non-zero conductivity even as the charge carriers change from electrons to holes (the neutrality point or the Dirac point). For most materials, as the charge carrier concentration tends towards zero, so does the conductivity, so that there is a metal to insulator transition
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at no temperatures. But graphene has shown no signs of a metal-insulator transition even down to liquid helium temperatures [35].

Fig 5.1: A plot of the Hall conductivity xy (red) and the Hall resistivity xy (green) as a function of carrier concentration. Aside from the anomalous quantum Hall effect, one of the most exciting prospects for graphene is that it may eventually prove useful in electronic applications.We start studying about Graphene Transistors by comparing the normal FET characteristics to that of Graphene. Due to its high electronic quality, graphene has also attracted the interest of technologists who see them as a way of constructing ballistic transistors. Graphene exhibits a pronounced response to perpendicular external electric fields, allowing one to build FETs (field-effect transistors). Facing the fact that current graphene transistors show a very poor on-off ratio, researchers are trying to find ways for improvement. Researchers had demonstrated four different types of logic gates, each composed of a single graphene transistor and built an experimental graphene chip known as a frequency multiplier. It is capable of Graphene transistor taking an incoming electrical signal of a certain frequency and producing an output signal that is a multiple of that frequency.

Fig 5.2: Graphene Transistor Although these graphene chips open up a range of new applications, their practical use is limited by a very small voltage gain (typically, the amplitude of the output signal is about 40 times less than that of the input signal). Moreover, none of these circuits was still demonstrated to operate at frequencies higher than 25 kHz. Recently, researchers have been able to create graphene transistors with an on and
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off rate of 100 gigahertz, far exceeding the rates of previous attempts, and exceeding the speed of silicon. The 240 nm graphene transistors were made using extant silicon-manufacturing equipment, meaning that for the first time graphene transistors are a conceivable, though still fanciful, replacement for silicon. The ability to build high frequency transistors with graphene is possible because of the higher speed at which electrons in graphene move compared to electrons in silicon. Researchers are also developing lithography techniques that can be used to fabricate integrated circuits based on graphene. 5.2 GAS DETECTION: Graphene makes an excellent sensor due to its 2D structure. The fact that its entire volume is exposed to its surrounding makes it very efficient to detect adsorbed molecules. Molecule detection is indirect: as a gas molecule adsorbs to the surface of graphene, the location of absorption experiences a local change in electrical resistance. While this effect occurs in other materials, graphene is superior due to its high electrical conductivity (even when few carriers are present) and low noise which makes this change in resistance detectable. The operational principle of graphene gas detectors is based on changes in their electrical conductivity, due to gas molecules adsorbed on graphene's surface and acting as donors or acceptors, similar to other solid-state sensors. However, the following characteristics of graphene make it possible to increase the sensitivity to its ultimate limit and detect individual dopants. First, graphene is a strictly two-dimensional material and, as such, has its whole volume exposed to surface adsorbates, which maximizes their effect. Second, graphene is highly conductive, exhibiting metallic conductivity and, hence, low Johnson noise even in the limit of no charge carriers, where a few extra electrons can cause notable relative changes in carrier concentration, n. Third, graphene has few crystal, which ensures a low level of excess (1/f) noise caused by their thermal switching. Fourth, graphene allows four-probe measurements on a single-crystal device with electrical contacts that are ohmic and have low resistance. All of these features contribute to make a unique combination that maximizes the signal-to-noise ratio to a level sufficient for detecting changes in a local concentration by less than one electron charge, e, at room temperature [36]. Graphene-based gas sensors allow the ultimate sensitivity such that the adsorption of individual gas molecules could be detected. Large arrays of such sensors would increase the catchment area , allowing higher sensitivity for short-time exposures and the detection of active (toxic) gases in as minute concentrations as practically desirable. The epitaxial growth of few-layer graphene offers a realistic promise of mass production of such devices. Our experiments also show that graphene is sufficiently electronically quiet to be used in single-electron detectors operational at room temperature and in ultrasensitive sensors of magnetic field or mechanical strain, in which the resolution is often limited by 1/f noise [37]. 5.3 GRAPHENE NANORIBBONS: Graphene nanoribbons (GNRs) are essentially single layers of graphene that are cut in a particular pattern to give it certain electrical properties. Depending on how the un-bonded edges are configured, they can either be in a zigzag or armchair configuration [38]. Calculations based on tight binding predict that zigzag GNRs are always metallic while armchairs can be either metallic or semiconducting, depending on their width. However, recent density functional theory calculations show that armchair nanoribbons are semiconducting with an energy gap scaling with the inverse of the GNR
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width. Indeed, experimental results show that the energy gaps do increase with decreasing GNR width. Zigzag nanoribbons are also semiconducting and present spin polarized edges. However, as of February 2008, no experimental results have measured the energy gap of a GNR and identified the exact edge structure. Zigzag nanoribbons are also semiconducting and present spin-polarized edges. Their 2D structure, high electrical and thermal conductivity, and low noise also make GNRs a possible alternative to copper for integrated circuit interconnects. Some research is also being done to create quantum dots by changing the width of GNRs at select points along the ribbon, creating quantum confinement [39]. 5.4 TRANSPARENT ELECTRODES: Optically transparent conductive materials are essential components for making electrical contacts in touch-sensitive screens, liquid crystal displays and solar cells. Graphene is a planar honeycombed structured carbon sheet which shows potential for these applications. However, the production of large areas of high quality graphene is a challenge. Current approaches to graphene synthesis include mechanical or chemical peeling of three-dimensional graphite crystals. However, repeated peeling introduces structural defects into the graphene sheets. Other methods based on the high-temperature decomposition of silicon carbide are only able to produce small samples [40]. Now, Byunh Hee Hong at Sungkyunkwan University, Korea, and collaborators have devised a method to grow graphene films on a large scale by depositing carbon onto substrates covered with a thin layer nickel.The researchers first deposited a thin 300-nanometer nickel (Ni) film on a silicon oxide support. Next, the Ni film was exposed to a hot gaseous mixture of methane/hydrogen, which generated graphene films containing up to ten sheets.The graphite was thinned down to graphene by controlling the initial thickness of the Ni film, growth temperature, and ratio and concentration of the gases.

Fig 5.3: Future applications of graphene based transparent electrodes Actually, the only difference between graphene and graphite is the number of layers, says Hong. The roughness and thickness of nickel films are very important parameters for the growth of thinner and better graphene layers.This optimised multilayer deposition led to easy-to-transfer, rippled graphene films with exceptional electrical conductivity and optical transparency. The nickel layer shrinks more than graphene while cooling down, so the ripple structures are naturally formed to release the stress, says Hong. Notably, the ripples moderately compensate the strain exerted on the films on stretching, thereby enhancing their stretchability.
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The researchers developed two processes to isolate the films. In a wet-transfer process, they soaked the supported films into mild etchants to slowly dissolve the nickel layers and lift the graphene off the support. In the second process, they attached them to soft substrates before etching the metal away. This dry-transfer process allows the film size and shape to be tailored without requiring any additional lithography, providing an especially attractive avenue for graphene-based device production. The most soon-to-be realized application is the use of graphene as a conductive electrode. Excellent carrier mobility and electron conductivity mean that graphene will find many places in the electronics market. Currently, the touch screen and electrode fields are dominated by the use of indium tin oxide (ITO). When compared to graphene, ITO is easy to handle and tends to outperform graphene in terms of conductance and low sheet resistance at the current stage. However, graphene quality is expected to improve with the fine tuning of its synthesis process and its electrical properties are still at an acceptable level for several applications. Given this, graphenes mechanical resilience, flexibility, and high transparency play important roles in establishing graphene as the new revolutionary material to replace ITO [41].

5.4.1. TOUCH SCREENS/DISPLAY SCREENS: Researchers have found that graphene can replace diodes that are used in electronic device display screens. The use of graphene not only reduces the cost but eliminates the use of metals, which may make devices easier to recycle. As layers of graphene are so thin, the resulting electrodes are transparent; this makes the material ideal for use in applications such as portable displays. It would, be used to replace indium titanium oxide, which is expensive and inflexible. Demonstration of a graphene based touch screen first done by Bae et al, which renders a graphene based electronics market something quite realistic. A palm-sized touch screen was made with a CVD grown graphene sheet. Even when the graphene sheet was predominantly single layer (this corresponds to the achievement of ~97% transmittance), it showed remarkable resilience upon bending and when written on with a touch screen pen. Bolstered by the roll-to-roll production possibility of graphene sheets on a large scale and given the reliable performance of the graphene touch screen, such industrial advancements seem very much feasible [42]. 5.4.2. LED/OLED: As a transparent, highly conductive material, graphene has its niche in the light-emitting display (LED)/organic LED (OLED) and solar cell research fields as well. Primarily, graphene is used as an anode electrode in experimental OLED applications in an effort to replace ITO, which is brittle and relatively unstable at ambient conditions. Graphene not only fulfills its function as an anode but also allows an OLED to be entirely transparent and flexible, expanding the design and application horizon of OLED lighting. Typically, solution suspended reduced GO is spin coated onto a ridged substrate such as glass or is mixed with conducting polymer and spin coated onto flexible PET. Most of the current research shows that although the performance (light emit-ting efficiency, sheet resistance, electron leakage) is acceptable, graphene is still inferior when compared to ITO due to the rough-ness of the graphene sheet made from reduced graphene oxide (GO) and the uneven distribution of hole density. These shortcomings are expected to be overcome with improvements of graphene synthesis and doping techniques, which would result in production of uniform high quality graphene with minimum roughness, with less resistance and controlled, uniform hole distribution. Graphene can also replace ITO
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as a transparent current spreading layer in LED. The outcome of such a replacement is improved transparency in the blue and near-infrared light re-gions and increased stability in acid and bases, as ITO tends to have these limitations. The graphene in this application model was synthesized by large scale CVD; it allowed easy patterning of graphene layers and batch fabrication of LED devices, taking us a step near to mass production of LED [43]. 5.4.3 SOLAR CELLS: Graphene films have also been implemented to make flexible organic solar cells working as anodes.The resultant devices have achieved competitive performance compared with their counterparts that use ITO electrodes. It has been revealed the graphene based organic photovoltaic devices can survive at a harsh bending condition of up to 1380 and maintain their performance. On the contrary, devices with ITO-anodes were eliminated just at the bending condition at 36C.Researchers have found that the conductivity of graphene on flexible substrates has outstanding stability even after hundreds of bending cycles.Polymer solar cells have attracted considerable attention in the past few years owing to their potential of providing environmentally safe, flexible, lightweight, inexpensive and efficient solar cells. Especially, bulk-heterojunction solar cells consisting of a mixture of a conjugated donor and acceptor polymer is considered as a promising approach [44]. Various architectures for organic solar cells have been investigated in recent years. In general, for a successful organic photovoltaic cell four important processes have to be optimized to obtain a high conversion efficiency of solar energy into electrical energy: (i) Absorption of light; (ii) Charge transfer and separation of the opposite charges (iii) Charge transport (iv) Charge collection. To assure an efficient light absorption and charge transport, a window electrode should be transparent with good conductivity. Currently, Indium tin oxide (ITO) and fluorine doped tin oxide (FTO) have been widely used as window electrodes in optoelectronic devices. These metal oxides, however, appear to be increasingly problematic due to (i) the limited availability of the element indium on earth, (ii) their instability in the presence of acid or base, (iii) their susceptibility to ion diffusion into polymer layers, (iv) their limited transparency in the near-infrared region, and (v) the current leakage of FTO devices caused by FTO structure defects. The search for novel electrode materials with good stability, high transparency and excellent conductivity is therefore a crucial goal for optoelectronics. With high electrical conductivity, high carrier mobility, and high optical transmittance in the visible range of the spectrum, graphene materials have become a great candidate of transparent conductive films (TCFs) in photovoltaic devices.In particular, graphene's mechanical strength and flexibility are advantageous compared with ITO and FTO. Moreover, graphene films can be deposited from solution over large areas. In particular, the scalability of production and convenient processing of GO has led to its emergence as an important precursor for the fabrication of TCFs [45]. 5.5 SUPERCAPACITORS: As surface area to mass ratio of graphene is extremely high, one of the potential applications is efficient ultracapacitors. It is believed that graphene could be used to produce ultracapacitors which will have a greater energy storage density than what is currently available. Graphene also competes with its carbon relatives to make better supercapacitors. It is important that the material acting as electrochemical
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double layer used in the capacitor provide high specific surface area and high conductivity. Previously used activated carbon materials had high surface area but low conductivity. Carbon nanotube based supercapacitors also showed limitations of high contact resistance between carbon nanotube and the current collector. Using chemically reduced GO in hy-drazine, on the other hand, provided high conductivity, large specific surface area and chemical stability, resulting in specific capacitance of up to 205 F/g in aqueous electrolyte. Other supercapacitors were fabricated from chemically modified graphene with high surface area and achieved specific capacitances of 135 F/g and 247 F/g in aqueous electrolytes. Ultracapacitors with better performance than batteries are produced using graphene. These ultracapacitiors store electrons on graphene sheets, taking advantage of the large surface of graphene to provide increase the electrical power that can be stored in the capacitor. Researchers are projecting that these ultracapacitors will have as much electrical storage capacity as lithium ion batteries but will be able to be recharged in minutes instead of hours [46]. 5.6 BIO-DEVICES: Graphene's modifiable chemistry, large surface area, atomic thickness and molecularly-gatable structure make antibody-functionalized graphene sheets excellent candidates for mammalian and microbial detection and diagnosis devices. The most ambitious biological application of graphene is for rapid, inexpensive electronic DNA sequencing. Integration of graphene (thickness of 0.34 nm) layers as nano electrodes into a nanopore can solve one of the bottleneck issues of nanoporebased single-molecule DNA sequencing. the sensitive charge-carrier modulation of chemically modified graphene has allowed the development of bio-devices that can detect a single bacterium or that can sense DNA .For example, an attachment of a single bacterium on a fabricated biodevice results in the generation of 1400 conducting holes, which can be easily monitored. Layers of graphene that are only as thick as an atom could help make human DNA sequencing faster and cheaper. Harvard University and MIT researchers have shown that sheets of graphene could be a big improvement over membranes that are currently used for nanopore sequencing--a technique that promises to speed up and simplify the sequencing of long strands of DNA. Today's sequencing techniques involve chopping up DNA, making many copies of the pieces, and reading fluorescent molecules attached to them. This approach takes days and costs tens of thousands of dollars. In contrast, nanopore sequencing could, in theory, parse an entire human genome in a few hours. Nanopore sequencing involves pulling a DNA strand through a tiny hole in a membrane that's suspended in a salt solution with a voltage applied across it. Ions moving from one side of the membrane to the other create an electric current. As each of four different DNA bases passes through the pore, the current strength decreases to a different extent, making it possible to rapidly sequence the bases.The nanopores currently used for DNA sequencing are typically made from bacterial proteins or are etched in silicon-nitride membranes. Such membranes are 20 to 30 nanometers thick. But since the distance between two DNA bases is 0.5 nanometers, 40 to 60 bases could be stuck in the pore at a time. A thinner membrane, such as graphene, might allow for more accurate base identification. A single layer of graphene is just one nanometer thick. The researchers create their membrane by placing a graphene flake over a 200-nanometer-wide opening in the middle of a silicon-nitride surface. Then they drill a few pores, just nanometers wide, in the graphene with an electron beam. The membrane is finally immersed in a salt solution that's in contact
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with silver electrodes. The researchers observed dips in the current when a DNA strand passed through the pore, showing that the method could eventually be used to identify DNA bases.Identifying individual DNA bases as they pass through the pore will take much more work, however. Each of the four different DNA bases should block the current passing through the pore by a different amount. Any device should be able to distinguish these varying amounts. But doing that will mean precisely controlling the speed with which DNA flies through the pore. Such control is the biggest hurdle to making nanopore sequencing practical. Each DNA molecule, containing thousands of bases, passes through the pore in hundreds of microseconds (about four nanoseconds per base). To read a single base, one at a time, would mean the strand would have to be in the pore more than 1,000 times longer.These can hold molecules for tens of milliseconds, but are less stable than silicon nitride and graphene [46]. 5.7 SENSORS AND ACTUATORS: In medical field, as sensors to diagnose diseases. These sensors are based upon distinctive property of graphene's large surface area and the fact that molecules that are sensitive to particular diseases can very well attach to the carbon atoms in graphene. For example, researchers have found that strands of DNA, graphene, and fluorescent molecules can be combined to diagnose various diseases. Owing to the cornucopia of fascinating properties that it has beyond merely its electrical ones, graphene shows an interest-ing variety of applications in the field of sensors and actuators. Just to take a few examples, graphenes negative thermal expansion coefficient makes possible the fabrication of a microactuator that can be used to imitate biological movements. Zhu attached a patterned CVD grown graphene sheet to epoxy (with positive thermal coefficient), making a micro cantilever. When heat was provided from an electrical current, the difference in thermal expansion made the cantilever bend up and back down. This was further elaborated by the imitation of dragonfly wings made to move with the same concept. Another study discovered graphene actuation induced by the strain from an electrostatic double layer under aqueous conditions. This demonstrated a possible use of monolayer graphene for nano electro-mechanical system actuators. Lastly, Wang et al fabricated highly sensitive strain sensors using graphene ripples. By applying graphene strips to a pre-strained PDMS substrate, they created evenly distributed graphene nano ripples. The sensor utilizes the fact that nano ripples (commonly viewed as defects in CVD grown graphene) increase the sheet resistance of the graphene due to the electron scattering that occurs at the ripples. Thus the strain sensing is done by monitoring the sheet resistance change with the changing strain that disturbs the nano ripple formations [47]. 5.8 INTEGRATED CIRCUITS: Graphene has the ideal properties to be an excellent component of integrated circuits. Graphene has a high carrier mobility, as well as low noise, allowing it to be used as the channel in a FET. The issue is that single sheets of graphene are hard to produce, and even harder to make on top of an appropriate substrate. Researchers are looking into methods of transferring single graphene sheets from their source of origin onto a target substrate of interest. The smallest transistor so far, one atom thick, 10 atoms wide was made of graphene. Researchers have fabricated and characterized graphene transistors operating at GHz frequencies. They have also announced to have created an n-type transistor, which means that both n and p-type transistors have now been created with graphene. At the same time, the researchers demonstrated the

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first functional graphene integrated circuit a complementary inverter consisting of one p- and one ntype graphene transistor. However, this inverter also suffered from a very low voltage gain [48]. 5.9 ANTI-BACTERIAL APPLICATIONS: Scientists have also found that sheets of graphene oxide are highly effective in killing bacteria such as Escherichia coli. This means graphene could be useful in applications such as hygiene products or packaging that will help keep food fresh for longer [49]. 5.10 T-RAY SCANNERS: Terahertz radiation, or T-rays, are particularly well-suited for detecting hidden objects at airport security checkpoints without the health risk posed by X-rays. T-rays could also serve as the basis for medical scanning devices that come even closer to the "Star Trek" tricorder. T-ray scanning is already being used for skin-cancer screening and tooth-cavity detection. The fast frequencies that can be achieved using graphene circuits are the basis for chemical sensors and for generators of terahertz-range light. Maybe graphene will hasten the arrival of those brave new T-ray scanners, for better or worse [50]. 5.11 HEAT CONDUCTING GRAPHENE TO COOL ELECTRONICS GADGETS: Overheating in laptops and electronic gadgets isn't just an annoyance to the end user, it's a major technological hurdle that puts a hard limit to the speed and energy efficiency of electronics. Heating in electronic components is inevitable and, as processing speeds grow exponentially, a central problem that needs to be dealt with using constantly improving technology. While heat-dissipating fans and the increasingly popular water cooling systems may do the job for now, more portable (and/or quieter) solutions are needed. Silicon, an invaluable material for its unique electronic properties, doesn't however have good thermal properties, particularly at the nanometer scale. A new, promising approach to controlling the heat problem is therefore to incorporate materials with superior thermal properties into silicon computer chips, to make the heat transfer swifter and more efficient. Knowing that graphene behaves as a strong heat conductor can dramatically improve the thermal characteristics, meaning lower temperatures and a concrete possibility for chip manufacturers to reach higher processing speeds with relative ease. Recently, a team of scientists from the University of California (USA) found that multiple layers of graphene show strong heat conducting properties that can be harnessed in removing dissipated heat from electronic devices [51]. 5.12 DETECTING LIGHT WITH GRAPHENE: Researchers have explored graphene's extraordinary electronic properties for numerous applications over the past few years, from superfast transistors to extremely dense memory chips. Now, for the first time, IBM researchers are exploiting graphene's unique properties for optoelectronics, using graphene sheets to make photodetectors.Light detectors are typically made using III-V semiconductors-materials made of multiple elements such as gallium and phosphorus. When light hits these materials, each photon absorbed creates an electron-hole pair, and the electrons are then shuttled out of the material to produce an electrical current [52]. Graphene--a sheet of carbon atoms linked in a honeycomb structure--transports electrons tens of times faster than III-V semiconductors. That means that graphene photodetectors could work at extremely high frequencies, making them highly efficient at detecting light and transporting the resulting
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electrons to an external circuit. The material also absorbs wavelengths ranging from visible to infrared, whereas thin layers of III-V semiconductors don't absorb many infrared frequencies. Graphene has already been used to make several kinds of transistors, including ultrahigh radiofrequency devices. The highly conductive atom-thick sheets could also replace expensive and brittle indium tin oxide as the electrode material in flexible flat-panel displays and thin solar cells. People are also considering graphene for ultracapacitor electrodes and for dense and superfast computer memory [53]. Yet despite all these electronic applications, many experts considered graphene less than ideal for optical devices. This is because the electrons and holes generated by incoming photons normally combine in graphene within tens of picoseconds, leaving no free electrons for current. This also happens in a metal. But the speed with which the charged particles travel in graphene is key.If we can have some kind of an electric field to separate the electron-hole pairs, we can collect them fast enough. It is already known that when metal contacts are deposited on graphene, electric fields are generated at the interface between the two materials. So the researchers took advantage of this field. Their device is a piece of multilayered graphene with metal contacts on top. When they shine light near the contact, the field separates the electrons and holes, and a current is generated [54].

Fig 5.4: Light detector A graphene photodetector takes advantage of the electric field that is created at the interface between metal contacts (gold) and graphene. When light falls on graphene, the field helps to separate electrons from holes, leading to an electric current. A single sheet of graphene absorbs 2.3 percent of the light falling on it, a significant amount for a one-atom-thick material. You have a photodetector that has a number of advantages: it absorbs over a wide wavelength range, it's very fast, it has a high absorbance, it's a single atomic layer.This combination makes it rather unique. Ultrafast photodetectors could find use in future optical communications networks with data rates beyond 40 gigabits per second; right now, optical networks have data rates of about 10 gigabits per second. The photodetectors could also be used in optical computers that compute with electrons but
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transfer data using light instead of sending it over heat-prone copper wires. Graphene would also make a better detector for terahertz radiation, which has shown promise for medical and security imaging.The researchers get current in response to light pulses at a frequency of 40 gigahertz. Frequencies higher than this are not possible with today's electronics but graphene could, in theory, enable photodetectors that work at frequencies even higher than 0.5 terahertz. 5.13 GRAPHENE TRANSISTORS OPERATING IN THREE MODES FOR COMMUNICATIONS: A single graphene transistor that does the job of many conventional ones could lead to compact chips for cell phones. Researchers have already made blisteringly fast graphene transistors. Now they've used graphene to make a transistor that can be switched between three different modes of operation, which in conventional circuits must be performed by three separate transistors. These configurable transistors could lead to more compact chips for sending and receiving wireless signals.Chips that use fewer transistors while maintaining all the same functions could be less expensive, use less energy, and free up room inside portable electronics like smart phones, where space is tight. The new graphene transistor is an analog device, of the type that's used for wireless communications in Bluetooth headsets and radio-frequency identification (RFID) tags [55].

Fig 5.5: Triple transistor: Single graphene transistors like this one can be made to operate in three modes and perform functions that usually require multiple transistors in a circuit. Graphene's perfect structure at the atomic level provides smooth sailing for electrons, and the material conducts electrons better than any other materials do at room temperature. So far, it's been used to make transistors that switch at about 100 gigahertz, or 100 billion times per second, 10 times faster than the best silicon transistors; it's predicted the material could be made into transistors that are even 1,000 times faster than this. And because graphene is smooth and flat, it should be compatible with the chip-making equipment at semiconductor fabs.But graphene offers other properties besides just being a great conductor of electrons. It's also possible to change the behavior of a graphene transistor on the fly, something that can't be done with conventional silicon transistors. The transistors that make up conventional silicon logic circuits can only behave in one of two ways, called "n" for negative or "p" for positive--they either control the flow of electrons or the flow of "holes," or positive charges. Whether a conventional transistor is p-type or n-type is determined during fabrication. But graphene is ambipolar: it can conduct both positive and negative charges [56].

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By changing the voltage applied to a sheet of graphene using three electrical gates, they could switch the graphene between three different modes: n-type, p-type, and a mode where it conducted positive and negative charge equally. This triple-mode transistor acts as an amplifier and can be used to encode a data stream by changing the frequency and the phase of a signal. Changes in phase and frequency are used to encode data in telecommunications devices such as Bluetooth headsets and RFID tags. This device is the first that can do this level of signal processing in a single transistor. Usually such signaling requires multiple transistors. Their transistor is a proof-of-concept device it demonstrates what might be possible with graphene.Other groups have demonstrated multimode transistors using graphene, carbon nanotubes, and organic molecules. The researchers say that the new graphene triplemode circuit can be controlled better than those devices.Control is critical when designing transistors that are ambipolar. People used to consider ambipolarity a bad thing because it's typically difficult to control how an ambipolar transistor will behave, which makes it difficult to use them at all [57].

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CHAPTER 6 CONCLUSIONS & REFERENCES

CONCLUSIONS: In this report, the preparation, properties, and applications of graphene-based materials have been reviewed. Preparation of high quality graphene materials in a cost effective manner and on the desired scale is essential for many applications. Graphene nanoelectronics is an emerging area of research. The 2010 Nobel Prize for physics was awarded to A. Geim and K. Novoselov for the discovery of graphene and its unexpected physical properties, paving the way for many new applications in the area of nanoelectronics, nanooptics, and solid state physics.CVD growth on metal foils has exceptional potential for, ultimately, the production of endless lengths of graphene/nlayer graphene of desired widths (graphene foil) that could then be picked up by roll-to-roll processing. Further improvement of the quality along with development of a clean transfer process for such foils will help to realize many applications including graphene-based electronic devices, for thermal management, for transparent conductive electrodes, and others. Fine control of the number of graphene layers for n-layer graphene (with the exception of monolayer graphene) is an important challenge for the materials community, such as for fundamental studies of bi-layer and tri-layer graphene, and to understand the performance as TCFs. The preparation of graphene materials via chemicalprocessing routes (e.g., oxidation of graphite followed by reduction of the graphene oxide platelets obtained by exfoliation) may be able to produce fairly large amounts of graphene cost effectively;however, the chemical details (e.g., oxidation/reduction mechanisms and detailed chemical structures) need to be more fully understood. Future efforts for graphene and n-layer graphene such as achieving desired surface functionalization, and, e.g., the cutting or preparation into desired shapes, could generate novel structures having many applications. FUTURE WORK: The biggest challenge in exploiting graphenes jack-of-all-trades flexibility in computing applications is getting it to perform as a true semiconductor. While it can be considered a semiconductor like silicon, graphene lacks one crucial propertythe ability to act as a switch. Without this, a chip will draw electricity continuously, unable to turn off. But engineers are making headway.Researchers at the University of Illinois showed that nano ribbons of graphene could be cut in such a way that they could be turned on and off. The most likely applications for grapheme will be in analog systems, such as radar, satellite communications, and imaging devices. The first graphene device from DARPA will be for specialized government communications. Researches envision graphene transistors amplifying signals between cell towers and eventually inside cell phones. Even in analog devices, there are still hurdles to overcomemost notably the difficulty of creating large batches of graphene.

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