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GRAPHENE :

1. INTRODUCTION Graphene is a flat monolayer of carbon atoms tightly packed into a two-dimensional(2D) honeycomb lattice, and is a basic building block for graphitic materials of allother dimensionalities. It can be wrapped up into 0D fullerenes, rolled into 1Dnanotubes or stacked into 3D graphite.Previously, graphene was also defined in the chemical literature as follows: A singlecarbon layer of the graphitic structure can be considered as the final member of theseries naphthalene, anthracene, coronene, etc. and the term graphene should thereforebe used to designate the individual carbon layers in graphite intercalation compounds.Use of the term "graphene layer" is also considered for the general terminology of carbons.The IUPAC compendium of technology states: "previously, descriptions such asgraphite layers, carbon layers, or carbon sheets have been used for the termgraphene...it is not correct to use for a single layer a term which includes the termgraphite, which would imply a threedimensional structure. The term graphene shouldbe used only when the reactions, structural relations or other properties of individuallayers are discussed." In this regard, graphene has been referred to as an infinitealternant (only six-member carbon ring) polycyclic aromatic hydrocarbon (PAH). Thelargest molecule of this type consists of 222 atoms and is 10 benzene rings across. Ithas proven difficult to synthesize even slightly bigger molecules, and they still remain"a dream of many organic and polymer chemists". Furthermore, ab initio calculationsshow that a graphene sheet is thermodynamically unstable with respect to otherfullerene structures if its size is less than about 10 nm (graphene is the least stablestructure until about 6000 atoms.Also, a definition of "isolated or free standinggraphene" has recently been proposed: "graphene is a single atomic plane of graphite,whichand this is essentialis sufficiently isolated from its environment to beconsidered free-standing." This definition is narrower than the definitions given aboveand refers to cleaved, transferred and suspended graphene monolayers. Other forms of graphene, such as graphene grown on various metals, can also become free-standing if transferred to, e.g., SiO or suspended. A new example of isolated graphene isgraphene on SiC after its passivation with hydrogen.Before reviewing the earlier work on graphene, it is useful to define what 2D crystalsare. Obviously, a single atomic plane is a 2D crystal, whereas 100 layers should beconsidered as a thin film of a 3D material. But how many layers are needed to make a3D structure? For the case of graphene, the situation has recently become reasonablyclear. It was shown that the electronic structure rapidly evolves with the number of layers, approaching the 3D limit of graphite already at 10 layers20. Moreover, onlygraphene and, to a good approximation, its bilayer have simple electronic spectra:they are both zero-gap semiconductors (can also bereferred to as zero-overlap semimetals) with one type of electrons and one type of holes. For 3 and more layers, the spectra become increasingly complicated: Severalcharge carriers appear, and the conduction and valence bands start notablyoverlapping. This allows one to distinguish between single-, double- and few- (3 to<10)layer graphene as three different types of 2D crystals (graphenes). Thickerstructures should be considered, to all intents and purposes, as thin films of graphite.From the experimental point of view, such a definition is also sensible. The screeninglength in graphite is only 5 (that is, less than 2 layers in thickness) and, hence, onemust differentiate between the surface and the bulk even for films as thin as 5 layers.Earlier attempts to isolate graphene concentrated on chemical exfoliation. To this end,bulk graphite was first intercalated (to stage I) so that graphene planes becameseparated by layers of intervening atoms or molecules.This usually resulted in new 3D materials. However, in certain cases, large moleculescould be inserted between atomic planes, providing greater separation such that theresulting compounds could be considered as isolated graphene layers embedded in a3D matrix. Furthermore, one can often get rid of intercalating molecules in a chemicalreaction to obtain a sludge consisting of restacked and scrolled graphene sheets.Because of itsuncontrollable character, graphitic sludge has so far attracted onlylimited interest.There have also been a small number of attempts to grow graphene. The sameapproach as generally used forgrowth of carbon nanotubes so far allowed graphitefilms only thicker than 100 layers. On the other hand,single- and few-layer graphenehave been grown epitaxially by chemical vapour deposition of hydrocarbons onmetalsubstrates and by thermal decomposition of SiC. Such films were studied by surfacesciencetechniques, and their quality and continuity remained unknown. Only lately,few-layer graphene obtained on SiCwas characterized with respect to its electronicproperties, revealing high-mobility charge carriers. Epitaxialgrowth of grapheneoffers probably the only viable route towards electronic applications and, with somuch atstake, a rapid progress in this direction is expected. The approach that seemspromising but has not beenattempted yet is the use of the previously demonstratedepitaxy on catalytic surfaces (such as Ni or Pt)followed by the deposition of aninsulating support on top of graphene and chemical removal of the primarymetallicsubstrate. 2. GRAPHITIC MATERIALS Figure 2.1 Graphene forms the structural material for fullerines, carbon nano tubesand graphiteThe major graphitic materials are graphite, carbon nanotubes ,fullerenes or buckyballs. Graphene is a 2D building material for these carbon materials. It can bewrapped up into 0D buckyballs, rolled into 1D nanotubes or stacked into 3D graphiteas shown in the figure 2.1. Therefore graphene derives all the important propertiesthese materials. Hence it has got broader areas of applications compared to otherforms. But problem with graphene is that it is a 2D material. So it is very muchunstable in free standing form while other forms are found to be very muchstable.Sographene must be in supported form i.e. it must always have a substrate. Dueto the supported form its properties gets reduced.

3 . PRODUCTION TECHNIQUES 3.1 SCOTCH TAPE TECHNIQUE First, a flake of graphite wasplaced on some sticky-backedplastic. Then, the plasticwasfolded over itself and pulledapart repeatedly so that the flakebecame thinner andthinner as itwas worked on by the adhesive.Then, the plastic was attached toa silicon wafer and rubbed andit is at this point thatthe reallyimportant discoveries occurred.Figure 3.1.1 Scotch tape techniqueResearchers had tried to seek out graphene using the most powerful and sophisticatedmicroscopes, but found that their graphite residue interacted with the silicon oxide onthe wafers surface, leading to a change of colour according to the thickness of thatpart of the sample around 100 layers thick would yield yellow, but a monolayer of constituent graphene would yield an almost invisible pink.Moreover, these and otherthickness-based colour variations could be detected with a traditional lightmicroscope. 3.2 EPITAXIAL GROWTH ON SILICON CARBIDE Here a SiC substrate with Ni coated over it is taken. Then using the chemical vapourdeposition of carbonweobtain a Ni C layer. Then we go by two methods: First one is to etch Ni layer using FeCl solution. Thus we will get graphene floatingover the solution which is temporarily transferred to PDMS substrate. PDMS is polydimethyl siloxane.Another way is to etch SiO2 layer initially using Buffered oxide Etchant and thenobtaining floating Graphene after removing Ni layer. Then as said earlier the floatinglayer is transferred on to PDMS. Figure 2.2.1 shows how its done.Figure 3.2.1 Epitaxial growth on SiCFigure 3.2.2 Graphene on PDMS 3.3SODIUM REDUCTION OF ETHANOL A recent publication has described a process for producing gram-quantities of graphene, by the reduction of ethanol by sodium metal, followed by pyrolysis of theethoxide product, and washing with water to remove sodium salts. 3.4GRAPHENE FROM NANOTUBES Experimental methods for the production of graphene ribbons are reported consistingof cutting open nanotubes. In one such method multi walled carbon nanotubes are cutopen in solution by action of potassium permanganate and sulfuric acid. In anothermethod graphenenanoribbons are produced by plasma etching of nanotubes partlyembedded in a polymer filmFigure 3.4.1 Nano tubes cut open to form monolayer graphene 4. PROPERTIES 4.1 ATOMIC STRUCTURE& ELECTRONIC PROPERTIES The atomic structure of isolated, single-layer graphene was studied by transmissionelectron microscopy (TEM) on sheets of graphene suspended between bars of ametallic grid. Electron diffraction patterns showed the expected hexagonal lattice of grapheneGraphene sheets in solid form (density > 1 g/cm3) usually show evidence indiffraction for graphite's 0.34 nm a) Graphene layers b) Energy band structureIntrinsic graphene is a semimetal or zero-gap semiconductor. Understanding theelectronic structure of graphene is the starting point for finding the band structure of graphite. It was realized early on that the E-k relation is linear for low energies nearthe six corners of the two-dimensional hexagonal Brillouin zone, leading to zeroeffective mass for electrons and holesDue to this linear (or conical") dispersion relation at low energies, electrons and holes near these six points, behave likerelativistic particles described by the Dirac equation for spin 1/2 particles. Hence, theelectrons and holes are called Dirac fermions, and the six corners of the Brillouinzone are called the Dirac points. The equation describing the E-k relation is; where the Fermi velocity. 4.2 ELECTRONIC TRANSPORT Experimental results from transport measurements show that graphene has aremarkably high electron mobility at room temperature, with reported values in excessof 15,000 cm2Vs1. The mobility is nearly independent of temperature between10 K and 100 K. Scattering by the acoustic phonons of graphene places intrinsiclimits on the room temperature mobility to 200,000 cm2V1s1 at a carrier density of 1012cm2

. The corresponding resistivity of the graphene sheet would be 10 6c m , less than the resistivity of silver, the lowest resistivity substance known at roomtemperature. However, for graphene on silicon dioxide substrates, scattering of electrons by optical phonons of the substrate is a larger effect at room temperaturethan scattering by graphenes own phonons, and limits the mobility to 40,000 cm2V1s1 4.3 OPTICAL PROPERTIES Graphene's unique electronic properties produce an unexpectedly high opacity for anatomic monolayer, with a startlingly simple value: it absorbs 2.3% of white light,where is the fine-structure constant. This is "a consequence of the unusual low-energy electronic structure of monolayer graphene that features electron and holeconical bands meeting each other at the Dirac point This has been confirmedexperimentally, but the measurement is not precise enough to improve on othertechniques for determining the fine-structure constant. 4.4 SPIN TRANSPORT Graphene is thought to be an ideal material for spintronics due to small spin-orbitinteraction and near absence of nuclear magnetic moments in carbon. Electrical spin-current injection and detection in graphene was recently demonstrated up to roomtemperature.Spin coherence length above 1 micron at room temperature was observedand control of the spin current polarity with an electrical gate was observed at lowtemperature. 4.5 THERMAL PROPERTIES The near-room temperature thermal conductivity of graphene was recently measuredto be between (4.840.44)103to (5.300.48) 103Wm . These measurements,made by a non-contact optical technique, are in excess of those measured for carbonnanotubes or diamond. Potential for this high conductivity can be seen by consideringgraphite, a 3D version of graphene that has basal plane thermal conductivity of over a1000 W/mK (comparable to diamond). In graphite, the c-axis (out of plane) thermalconductivity is over a factor of ~100 smaller due to the weak binding forces betweenbasal planes as well as the larger lattice spacing. In addition, the ballistic thermalconductance of a graphene is shown to give the lower limit of the ballistic thermalconductances, per unit circumference, length of carbon nanotubes. 4.6 MECHANICAL PROPERTIES As of 2009, graphene appears to be one of the strongest materials ever tested.Measurements have shown that graphene has a breaking strength 200 times greaterthan steel. However, the process of separating it from graphite, where it occursnaturally, will require some technological development before it is economicalenough to be used in industrial processes, though this may be changing soon.Using an atomic force microscope (AFM), the spring constant of suspended graphenesheets has been measured. Graphene sheets, held together by van der Waals forces,were suspended over silicon dioxide cavities where an AFM tip was probed to test itsmechanical properties. Its spring constant was in the range 1-5 N/m and the Young'smodulus was 0.5 TPa, which differs from that of the bulk graphite. These high valuesmake graphene very strong and rigid. These intrinsic properties could lead to usinggraphene for NEMS applications such as pressure sensors and resonators. 5. APPLICATIONS IN ELECTRONICS 5.1 GRAPHENE TRANSISTORS Graphene is a single atom-thick layer of carbon atoms bonded in a hexagonalhoneycomb-like arrangement. This two-dimensional form of carbon has uniqueelectrical, optical, mechanical and thermal properties and its technologicalapplications are being explored intensely.Uniform and highquality graphene wafers were synthesized by thermaldecomposition of a silicon carbide (SiC) substrate. The graphene transistor itself utilized a metal top-gate architecture and a novel gate insulator stack involving apolymer and a high dielectric constant oxide. The gate length was modest, 240nanometers, leaving plenty of space for further optimization of its performance byscaling down the gate length.It is noteworthy that the frequency performance of thegraphene device already exceeds the cut-off frequency of state-of-the-art silicontransistors of the same gate length (~ 40 GigaHertz). Similar performance wasobtained from devices based on graphene obtained from natural graphite, proving thathigh performance can be obtained from graphene of different origins 10 Figure 5.1.1 (a) Optical image of the device layout with groundsignalground accessesfor the drain and the gate. (b) (False color)scanning electron microscopy image of thegraphene channel andcontacts. The inset shows the optical image of the as-depositedgraphene flake (circled area) prior to the formation of electrodes.(c) Schematic crosssection of the graphene transistor. Note that the device consists of two parallelchannels controlled by a singlegate in order to increase the drive current and devicetransconductanceFacing the fact that current graphene transistors show a very poor on-off ratio,researchers are trying to find ways for improvement. In 2008 researchers of AMICAand University of Manchester demonstrated a new switching effect in graphene field-effect devices. This switching effect is based on a reversible chemical modification of the graphene layer and gives an on-off ratio of greater than six orders of magnitude.These reversible switches could potentially be applied to nonvolatile memories.In 2009 researchers at the Politecnico di Milano demonstrated four different types of logic gates, each composed of a single graphene transistor. In the same year, theMassachusetts Institute of Technology researchers built an experimental graphenechip known as a frequency multiplier. It is capable of taking an incoming electrical signal of a certain frequency and producing an output signal that is a multiple of thatfrequency. Although these graphene chips open up a range of new applications, theirpractical use is limited by a very small voltage gain (typically, the amplitude of theoutput signal is about 40 times less than that of the input signal). Moreover, none of these circuits was demonstrated to operate at frequencies higher than 25 kHz.In February 2010, researchers at IBM reported that they have been able to creategraphene transistors with an on and off rate of 100 gigahertz, far exceeding the ratesof previous attempts, and exceeding the speed of silicon. The graphene transistorsmade at IBM were made using extant silicon-manufacturing equipment, meaning thatfor the first time graphene transistors are a conceivablethough still fancifulreplacement for silicon 5.2 GRAPHENE NANORIBBONS Graphenenanoribbons (GNRs) are essentially single layers of graphene that are cut ina 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.Calculations based on tight binding predict that zigzag GNRs are always metallicwhile armchairs can be either metallic or semiconducting, depending on their width.However, recent density functional theory calculations show that armchairnanoribbons are semiconducting with an energy gap scaling with the inverse of theGNR width. Indeed, experimental results show that the energy gaps do increase withdecreasing GNR width. However, as of February 2008, no experimental results havemeasured the energy gap of a GNR and identified the exact edge structure. Zigzagnanoribbons are also semiconducting and present spin polarized edges.Their 2D structure, high electrical and thermal conductivity, and low noise also makeGNRs a possible alternative to copper for integrated circuit interconnects. Someresearch is also being done to create quantum dots by changing the width of GNRs atselect points along the ribbon, creating quantum confinement.Figure 5.2.1 a)GNR having zizzag and arm chair structure b)Zigzag GNR carryingspin current . Zigzaggraphenenanoribbons could therefore serve as the basis for nanosizedspintronicdevices. 5.3 GRAPHENE BASED 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 asthe 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 lookinginto methods of transferring single graphene sheets from their source of origin(mechanical

exfoliation on SiO2 / Si or thermal graphitization of a SiC surface) onto atarget substrate of interest. In 2008, the smallest transistor so far, one atom thick, 10atoms wide was made of graphene.IBM announced in December 2008 that they havefabricated and characterized graphene transistors operating at GHz frequencies .Livermore National Laboratory announced that they have created an n-type transistor,which means that both and n and p-type transistors have now been created withgraphene. At the same time, the researchers at the Politecnico di Milano demonstratedthe first functional graphene integrated circuit a complementary inverter consistingof one p- and one n-type graphene transistor. However, this inverter also sufferedfrom a very low voltage gain.The ultimate goal would be an all-graphene circuit. This could be achieved by takingagraphene sheet and patterning the di_erent devices and leads by means of appropriate cutsthat would generate leads ribbons, dots, etc.. This papercuttingelectronics can have seriouslimitations with respect to reliability, scalability, and isprone to damaging and inducingdisorder in the graphenesheet . Therefore, in keepingwith the paper art analogy, wepropose an alternative origami electronics .We showhere that all the characteristics of graphene ribbons and dots (viz.geometricalquantization, 1D channels, surface modes) might be locally obtained bypatterning, notgraphene, but the substrate on which it rests. The essential aspect of ourapproach isthe generation of strain in the graphene lattice capable of changing the in-plane hoppingamplitude in an anisotropic way. This can be achieved by means of appropriate geometricalpatterns in an homogeneous substrate (grooves, creases, stepsor wells), or by means ofan heterogeneous substrate in which different regionsinteract differently with the graphenesheet, generating different strain proles. Anotherdesign alternative consists indepositing graphene onto substrates with regions that canbe controlably strained on demand. Through a combination of folding and/orclamping a graphene sheet onto such substratepatterns, one might generate local strainpro_les suitable for the applications discussed indetail below, while preserving awhole graphene sheet. 5.4 T R A N S P A R E N T C O N D U C T I N G E L E C T R O D E S Graphene's high electrical conductivity and high optical transparency make it acandidate for transparent conducting electrodes, required for such applications astouchscreens, liquid crystal displays, organic photovoltaic cells, and organic light-emitting diodes. In particular, graphene's mechanical strength and flexibility areadvantageous compared to indium tin oxide, which is brittle, and graphene films maybe deposited from solution over large areas. 5.4.1 GRAPHENE BASED LIQUID CRYSTAL DISPLAY Graphene is only one atom thick, optically transparent, chemically inert and an excellentconductor. These properties seem to make this material an excellent candidate forapplications in various photonic devices that require conducting but transparent thinfilms. In this letter we demonstrate liquid crystal devices with electrodes made of graphene which show excellent performance with a high contrast ratio. We also discussthe advantages of graphene compared to conventionally-used metal oxides in terms of low resistivity, high transparency and chemical stability. Graphene is the first example of truly two-dimensional materials 1 .Only one atom thick, it demonstrates high crystallographic quality 2 and ballistic electrontransport on the micrometer scale. Such unique properties make it a realistic candidate fora number of electronic applications. In particular, graphene is an attractive material foroptoelectronic devices, in which its high optical transmittance, low resistivity, highchemical stability and mechanical strength seems to make it an ideal optically-transparentconductor.Transparent conductors are an essential part of many optical devices. Traditionally, thinmetallic or metal-oxide films are used for these purposes (for a review see 3 ). At the sametime there is a constant search for new types of conductive thin films, as existingtechnologies are often complicated (e.g. thin metallic films require anti-reflection coating)and expensive (often using noble or rare metals). Furthermore, many of the widely usedmetal oxides exhibit nonuniform absorption across the visible spectrum and arechemically unstable (for instance the commonly used Indium Tin Oxide (ITO, In2O3:Sn)is known to inject oxygen5 and indium 6 ions into the active media of a device). Recentlycarbon nanotube films have been produced 7 and used as an alternative transparentconductor in various photonic devices including electric field-activated opticalmodulators, organic solar cells 8 and liquid crystal displays 9 . The experimental discoveryof grapheme brought a new alternative to the ubiquitous ITO. The optical properties of this material are now being widely tested., and graphene films have recently beenused as transparent electrodes for solar cells.The use of graphene as a transparentconductive coating for photonic devices and show that its high transparency and lowresistivity make this two-dimensional crystal ideally suitable for electrodes in liquidcrystal devices. We will also argue that graphene, being mechanically strong, chemically stable and inert, should improve the durability and simplify the technology of potentialoptoelectronic devices.Figure 5.4.1.1 (a) Schematic diagram of our liquid crystal devices with typical layerthicknesses in brackets: 1 glass (1mm); 2 graphene; 3 Cr/Au contact surroundinggraphene flake (5nm Cr + 50nm Au); 4 alignment layer (polyvinyl alcohol) (40 nm); 5 liquid crystal (20 alignment layer (40 nm); 7 ITO (150 nm); 8 glass (1 mm).The graphene flake is surrounded by a non-transparent Cr/Au contact. (b-e) Opticalmicrographs of one of our liquid crystal device using green light (505 nm, FWHM 23 nm)with different voltages applied across the cell: (b) V=8 Vrms; (c) V=13 Vrms; (d) V=22Vrms; (e) V=100 Vrms. Overall image indowis covered by graphene, surrounded by the opaque Cr/Au electrode. (f) An opticalmicrograph (in reflection, using white light) of a graphene flake on the surface of a 1 mmthickness glass slide. The contrast is of the order of 6%. Overall image width is slide. They were first located using an optical microscope(Figure 1f,g) and then furtheridentified as monolayer graphene using Raman microscopy. Thin (70 nm) chromium/goldcontacts were then deposited around the flakes, so the graphene crystal was effectivelycovering a window in the metallization, Figure 1a,b (this geometry also eliminates strayelectric fields from the edges of the electrode). A planar-aligned liquid crystal deviceswere then fabricated using such graphene-on-glass films as one of the transparentelectrodes, Figure 4.3.1.1. The other substrate was of a glass slide coated with conventional ITO. Both substrates were coated with a polyvinyl alcohol alignment layerwhich was subsequently baked and then unidirectionally rubbed (ITO-coated substrateonly) in order to promote uniform alignment of the liquid crystal director. The device wasthen capillary-filled with nematic liquid crystal material E7 (Merck). Applying a voltageacross the liquid crystal layer distorts the crystal alignment, changing the effectivebirefringence of the device and altering the transmitted light intensity. A control sample,with an opening in the metallization not covered by graphene, was also prepared (Figure1h). Note that although we will limit our consideration of graphene-based liquid crystaldevices by those with planar untwisted nematic liquid crystals, this technology couldequally be applied to any of the various nematic liquid crystal device types and also toferroelectric and other liquid crystal devices that use smectic phases. Figure 5.4.1.2 Light transmission through the liquid crystal device as a function of voltage applied across the cell, normalized to the maximum transmission. Inset: thesame at low voltages. Solid blue curve: in green light, 505 nm, FWHM 23 nm; dashedred curve: in white light An AC (square-wave) voltage was applied across the cells in order to reorient the liquidcrystal director. The electro-optic properties were observed using an optical microscopewith the device placed between crossed polarizers and the rubbing direction oriented 45 o

with respect to the polarizers. Above the expected threshold voltage of around 0.9 Vrms,a strong change in the transmission is observed (Figure 1b-e, 2) both in white andmonochromatic light. The fact that the whole electrode area changes contrast uniformlysuggests that the electric field is applied uniformly through the area of graphene and thatthe graphene has no negative effect on the liquid crystal alignment. The contrast ratio(between maximum transmission and the transmission when 100 Vrms is applied across 17 the cell) is better than 100 under illumination using white light, which is very good forthis type of cell and demonstrates that graphene could indeed be used effectively as atransparent electrode for liquid crystal displays. No significant changes in transmissionwere observed for the control sample, with only edge effects appearing due to the finitethickness of the cellWe will now assess the quality of our liquid crystal devices, concentrating on suchimportant issues as the transparency of graphene, its resistivity and chemical stability.Light absorption by graphene is presented as a function of the number of layers. Eachlayer of graphene absorbs about 2%, which is significantly lower than that of conventionally used ITO (15-18% ). Such high transmittance is explained by a lowelectronic density of states in graphene.Figure 5.4.1.3 Sheet resistance of a graphene device as a function of gate voltage with(solid red curve) and without (dashed blue curve) a layer of polyvinyl alcohol on top.Polyvinyl alcohol provides n-type doping, shifting the curve to negative gate voltages The sheet resistance of undopedgraphene is of the order of chemical doping and even unintentional doping (due to molecules absorbed from thesurrounding atmosphere, e.g. water) can be of the order of 1012cm-2). In liquid crystaldevices an electrode is usually in direct contact with an alignment layer (in our casepolyvinyl alcohol). We have tested the doping of graphene with polyvinyl alcohol, bypreparing a standard graphene device on a 300nm SiO2/Si wafer and measuring itsgate response with and without a layer of polyvinyl alcohol on top of graphene(Figure3). The introduction of a layer of polyvinyl alcohol produces n-type doping of about31012cm-2. For this particular sample it resulted in a drop in the sheet resistancedown to 400 transmission of about 98%. It is difficult to compare this result to ITO, as theresistance of In2O3 to obtain optical transmittance above 95%. ITO films with 95% transmittancedemonstrate comparable sheet resistances of a few hundred Ohms, dropping to tens of Ohms at an optical transmittance of about 90%.An important issue for most ITO-based liquid crystal devices and other photonicdevices is the chemical stability of the metal-oxide and the diffusion of ions into theactive media. Such processes deteriorate the active media (for example via oxidation if oxygen is injected) and can lead to breakdown at lower voltages. Furthermore, in liquidcrystal displays the injected ions get trapped at the alignment layer, thus screening theapplied electric field. This leads to the so-called image sticking problemwhich is usuallyavoided by driving the liquid crystal cells with alternating voltage. 5.4.2 ORGANIC LED & SOLAR CELLS USING GRAPHENE The graphene films can be prepared via either top-down exfoliation of graphite oxideflakes followed by thermal reduction, or bottom-up construction of extremely largePAHs, nanographene molecules followed by thermal fusion.To demonstrate how the transparent graphene films are potential window electrodes foroptoelectronics the Max-Planck scientists fabricated a dyesensitized solid solar cellusing the graphene film as anode and gold as cathode.Figure 5.4.2.1Illustration and performance of solar cell based on graphene electrodes. Shown is the dye-sensitized solar cell using graphene film as electrode, the four layersfrom bottom to top are gold, dye-sensitized heterojunction, compact titanium dioxide,and graphene film. (Image: Dr.Zhi/Max Planck Institute for Polymer Research)Thegraphene-based solar cells show a relatively lower efficiency than metal oxide coatingbased solar cells" he says. "There is still large room for improvement of the deviceperformance by, for example, further increasing the conductivity of the graphene filmsvia the use of large graphene sheets with lateral dimensions on the micrometer scale, orexploitation of a new and special structure of solar cells based on graphene windowelectrodes. Of course, we also face a number of challenges going forward, such asperfection of the graphene structure; a balance of conductivity and transparency of thegraphene film; fabrication techniques for graphene-based optoelectronics. In contrast to ITO, the graphene electrode shows an outstanding thermal and chemicalstability besides its high transparency and good conductivity. Furthermore, simpleprocessing enables inexpensive and large-scale industrial manufacturing. That is thereason why the concept of using graphene electrodes is emerging as a very practicableoption for future optoelectronic devices.The unique properties of the as-obtained graphene film include high conductivity, goodtransparency in both the visible and near infrared regions, ultra-smooth surface withtunable wettability, and high chemical and thermal stabilities, render the graphene-basedwindow electrodes versatile for applications not only in solar cells described in ourrecent work, but also in fabrication of flat panel displays, organic light-emitting diodes(OLEDs), and other modern optoelectronic devices.Figure 5.4.2.2Structure of graphene based OLED 5.5 ULTRA CAPACITORS Due to the incredibly high surface area to mass ratio of graphene, one potentialapplication is in the conductive plates of ultracapacitors. It is believed that graphenecould be used to produce ultracapacitors with a greater energy storage density than iscurrently available.With recent developments in power industry, increasing prices of energy and needs for storing energy from various new technologies, from regenerativebraking in electric and hybrid vehicles, ultracapacitors are playing critical role as theycan store and deliver energy in very short time unlike batteries. There has beentremendous research in this field to develop new materials which can store significantcharge using nanotechnology.Figure 5.5.1 Graphene based ultra-capacitorUniversity of Texas at Austin, mechanical engineering professor Rod Ruoff hasachieved a breakthrough in ultra-capacitors by using "graphene". Ruoff says,Graphenes surface area of 2630 m2/gram (almost the area of a football field inabout 1/500th of a pound of material) means that a greater number of positive ornegative ions in the electrolyte can form a layer on the graphene sheets resulting inexceptional levels of stored charge. After about nine months of research with thenew material, they have shown storage abilities similar to those of ultracapacitorsalready on the market, and they believe graphene'sultra thin structure will allow for sheets of the material to be stacked to increase energy storage and possibly double thecurrent capacity of ultra-capacitors. This would allow ultracapacitors to expand intomany other renewable and clean energy storage application 5.6 GRAPHENE BASED MEMORY DEVICES Graphene, a flat sheet of hexagonally arranged carbon atoms, can transportelectronsvery quickly. This has made it a promising material for high radio-frequencylogiccircuits, transparent electrodes for flexible flat-panel displays, and high-surface-areaelectrodes for ultracapacitors.Now researchers at the National University of Singapore have made computer memorydevices using graphene.This is the first step toward memory that could be muchdenser and faster than themagnetic memory used in today's hard drives. Theresearchers have made hundreds of prototype graphene memory devices, and theywork reliably, according toBarbaros zyilmaz, the physics professor who led the workpresented at a recentAmerican Physical Society meeting in Pittsburgh. "Graphene isgoing to change theelectronic industry," he says. "What was missing was a way to usegraphene as amemory element. So far there was almost no interest because it wasn't[thought]doable."The key to making memory elements is a material that can have two differentstates.That is because computer memory is stored as two bits: 1 and 0. Hard drivesalso needto be nonvolatile, which means the material should be able to hold on tothose stateswithout requiring power. Today's hard disks are made of magnetic cobaltalloys, andthey store bits as one of two magnetic orientations of a small area on thedisk.zyilmaz and his colleagues came up with an easy way to make graphene holdits twodifferent levels of conductivity, or resistance. Switching between these levelsrequiresapplying and removing an electric field. The researchers deposit a thin layerof aferroelectric material on top of the

graphene. Ferroelectrics have an intrinsic electricfield, and applying a voltage changes the direction of the field. The ferroelectric'sfieldhelpsgraphene sustain its conductivity. And, zyilmaz explains, "we can change thepolarization of the ferroelectric, which in turn changes the conductivity of graphene."The new memory idea is "thrilling because it's very simple," says Andre Geim, professor of physics at the University of Manchester, UK, who first isolated graphenesheets from graphite. "Ferroelectrics are well known. It's also known that an electricfield changes graphene's resistivity by a factor of typically 10. [zyilmaz] combinesthose two very well-known facts."Graphene memory would have significantadvantages over today's magnetic memory.Bits could be read 30 times faster becauseelectrons move through graphene quickly.Plus, the memory could be denser. Bit areason hard disks are currently a few tens ofnanometers across. At densities of 1 terabitper square inch, they will be about 25nanometers across, too small to hold theirmagnetization direction. With graphene, bitscould shrink to 10 nanometers or evensmaller. In fact, the memory devices wouldwork better with smaller graphene areas. 5.7 SINGLE MOLECULE GAS DETECTION It is shown using density functional theory that the trapping of molecules betweengraphene electrode plates can be used to sense molecules through their vibrationalfluctuations. This hypothesis is tested using water trapped in two graphene moleculesconnected to a potential difference. The electric current fluctuations generatedthrough the junction correspond to the fluctuations of the vibrational modes. Sincethis system yield currents in a range workable by present electronic devices, there isno need for further 'molecular amplification'. Fluctuations of the three modes of wateryield similar changes of potentials in the neighbourhood accessible to othermolecules; therefore, vibrations from a single water molecule, as an example, orvibrations from any other molecule can be transduced into electrical currents of magnitude compatible with present silicon technology. In the particular case of thewater molecule, a rectified potential signal is obtained from the fluctuations of theantisymmetric stretching mode and a simple transduction is obtained from thesymmetric stretching and bending modes. It is argued that the high sensitivity is dueto the strong delocalization of the frontier molecular orbitals or molecular plasmonson graphene electrodes, which guarantees the detection based on molecular potentialsor molecular vibrations; these plasmon-like molecules are of major importance for thedevelopment of molecular and nano electronics. 6. DEMERITS OF GRAPHENE 6.1 ZERO BAND GAP Graphene has got zero energy band gap. It means that it act as metal. This is the casewith a single layer of Graphene.Recently it has been demonstrated that the bandgapof graphene can be tuned from 0 to 0.25 eV (about 5 micron wavelength) by applyingvoltage to a dual-gate bilayer graphenefield-effect transistor (FET) at roomtemperature.One of the most unusual features of single-layer graphene (top) is that its conicalconduction and valence bands meet at a point -- it has no bandgap. Symmetricalbilayer graphene (middle) also lacks a bandgap. Electrical fields (arrows) introduceasymmetry into the bilayer structure (bottom), yielding a bandgap ( selectively tuned. Credit: Lawrence Berkeley National LaboratoryWang, who is also an assistant professor in the Department of Physics at theUniversity of California at Berkeley, has achieved just that. He and his colleagueshave engineered a bandgap in bilayer graphene that can be precisely controlled from 0to 250 milli-electron volts (250 meV, or .25 eV).Moreover, their experiment was conducted at room temperature, requiring norefrigeration of the device. Among theapplications made possible by thisbreakthrough are new kinds of nanotransistors and - because of its narrowbandgap - nano-LEDs and othernanoscaleoptical devicesin the infraredrange.Figure 6.1.1 By applying a fieldperpendicular to a bilayer graphene it gets atunable band gap 6.2 NON AVAILABILITY OF LARGE SCALE PRODUCTION TECHNIQUES Graphene is a relatively new material with outstanding electrical, chemical andmechanical properties that make it an attractive material for use as flexible conductorsof the sort used in gadgets such as touch screens and flat panel TVs. In the pastattempts to make large films of graphene have been unsuccessful, but now a team of scientists from South Korea and Japan have succeeded in roll-to-roll production of graphene films, growing them by chemical vapor deposition onto flexible coppersubstrates. The researchers grew their graphene sheets by chemical vapor deposition onto largesheets of copper foil. They coated the graphene with a thin layer of adhesive polymerand then dissolved away the copper backing. Using rollers, the graphene was thenpressed against another substrate, such as PET, and the polymer layer was removedby heating, leaving a film of graphene. They repeated the process to produce a sheetof four layers of graphene on top of each other. This four-layer sheet was then treatedwith nitric acid to improve its electrical conductivity.Figure 6.2.1 Large scale production of grapheneSo if we can find more ways to obtain large sheets of graphene then we can easilyover come all the demerits associated with graphene.Another problem with grapheneis that it is a 2D material. So it is very much unstable in free standing form whileother forms are found to be very much stable.Sographene must be in supported formi.e. it must always have a substrate. Due to the supported form its properties getsreduced. 7. FUTURE POSSIBILITIES OF GRAPHENE Despite the reigning optimism about graphene-based electronics, grapheniummicroprocessors are unlikely to appear for the next 20 years. In the meantime, one cancertainly hope for many other graphene-based applications to come of age.The most immediate application for graphene is probably its use in compositematerials. Indeed, it has been demonstrated that a graphene powder of uncoagulatedmicron-size crystallites can be produced in a way scaleable to mass production. Thisallows conductive plastics at less than 1 volume percent filling, which in combinationwith low production costs makes graphene-based composite materials attractive for avariety of uses. However, it seems doubtful that such composites can match themechanical strength of their nanotube counterparts because of much strongerentanglement in the latter case.Another enticing possibility is the use of graphene powder in electric batteries that arealready one of the main markets for graphite. An ultimately large surface-to-volumeratio and high conductivity provided by graphene powder can lead to improvements inbatteries efficiency, taking over from carbon nanofibres used in modern batteries.Carbon nanotubes have also been considered for this application but graphene powderhas an important advantage of being cheap to producer.One of the most promisingapplications for nanotubes is field emitters and, although there have been noreportsyet about such use of graphene, thin graphite flakes were used in plasma displays(commercialprototypes) long before graphene was isolated, and many patents werefiled on this subject. It is likely thatgraphene powder can offer even more superioremitting properties.. Spin-valve and superconducting field-effect transistors are alsoobvious research targets, and recent reports describing a hystereticmagnetoresistanceand substantial bipolar supercurrents91 prove graphenes majorpote ntial for these applications. An extremely weak spin-orbit coupling and theabsence of hyperfine interaction in C-graphene make it an excellent if not idealmaterial for making spin qubits. This guarantees graphene-based quantumcomputation to become an active research area. Finally, we cannot omit mentioninghydrogen storage, which has been an active but controversial subject for nanotubes. Ithas already been suggested that graphene is capable of absorbing an ultimately largeamount of hydrogen, and experimental efforts in this direction are duly expected. 8. CONCLUSION Graphene is a rapidly rising star on the horizon of materials science and condensedmatter physics. Thisstrictly two-dimensional material exhibits exceptionally highcrystal and electronic quality and, despite itsshort history, has already revealed acornucopia of new physics and potential applications,few of which were discussedhere. Whereas one can be certain of the realness of applications only whencommercialproducts appear, graphene no longer requires any further proof of itsimportance in terms offundamental physics. Owing to its unusual electronic spectrum,graphene has led to the emergence of anew paradigm of relativistic condensedmatter physics, where quantum relativistic phenomena, some of which are unobservable in high energy physics, can now be mimicked and tested intable-top experiments.More generally, graphene represents a conceptually new class of

materials that areonly one atom thickand, on this basis, offers new inroads into low-dimensionalphysics that has never ceased to surprise andcontinues to provide a fertile ground forapplications.

1.Graphene-based nanotechnology in energy applications


Graphene-based nanomaterials have many promising applications in energy-related areas. Just some recent examples: Graphene improves both energy capacity and charge rate in rechargeable batteries; activated graphene makes superior supercapacitors for energy storage; graphene electrodes may lead to apromising approach for making solar cells that are inexpensive, lightweight and flexible; and multifunctional graphene mats are promising substrates for catalytic systems.These examples highlight the four major energy-related areas where graphene will have an impact: solar cells, supercapacitors, lithium-ion batteries, and catalysis for fuel cells. A recent review in Small ("Chemical Approaches toward Graphene-Based Nanomaterials and their Applications in Energy-Related Areas") gives a brief overview of the recent research concerning chemical and thermal approaches toward the production of well-defined graphene-based nanomaterials and their applications in energy-related areas. The authors note, however, that before graphene-based nanomaterials and devices find widespread commercial use, two important problems have to be solved: one is the preparation of graphene-based nanomaterials with well-defined structures, and the other is the controllable fabrication of these materials into functional devices.The review's authors, led by Linjie Zhi, a professor in physical chemistry at the National Center for Nanoscience and Technology in Beijing, first discuss current research activities utilizing chemical approaches towards graphene-based nanomaterials. Then they specifically address graphene's use in energy-related areas including solar cells, lithium ion batteries, supercapacitors,

and catalysis. Schematic models of chemical strategies towards graphene from different carbon sources. (Reprinted with permission from Wiley-VCH Verlag)Solar cellsThe reviewers point out that graphene has great potential to be used for low-cost, flexible, and highly efficient photovoltaic devices due to its excellent electron-transport properties and extremely high carrier mobility. "Recently, several graphene-based solar cells have been reported, in which graphene serves as different parts of the cell. One of the reasons for the current interest in graphene is the great potential for transparent and conductive electrodes in solar cells. Graphene is an ideal 2D material which can be assembled into film electrodes with good transparency, high conductivity, and low roughness."After discussing various synthesis routes to fabricate transparent conductive electrodes for solar cells, the authors note that graphene also has other attractive properties for photovoltaic devices: "For example, graphene has been incorporated into conjugated polymers to improve the exciton dissociation and the charge-transport properties of the materials. Additionally, graphene also has potential to be used as photoactive material, since its bandgap and band-position can be induced and tuned via chemical functionalization or by controlling the size of the graphene sheets."Lithium-ion batteriesThe energy densities and performances of rechargeable lithium ion batteries which are used widely in portable electronics such as cell phones, laptop computers, digital cameras, etc. largely depend on the physical and chemical properties of the electrode materials. Thus, many research attempts have been made to design novel nanostructures and to explore new electrode materials in order to achieve higher capacity and to increase the battery's charge rate, increasingly also employing graphene in form of nanosheets, paper, and carbon nanotube or fullerene hybrids (for a detailed review see here: "Graphene-based electrode materials for rechargeable lithium batteries").SupercapacitorsDue to its superb characteristics of chemical stability, high electrical conductivity, and large surface area, graphene has been proposed as a competitive material for supercapacitor applications.The authors note that "in contrast to the conventional highsurface-area materials, the effective surface area of graphene materials as capacitor electrodes does not depend on the distribution of pores in a solid state, which is different from the current supercapacitors fabricated with activated carbons and carbon nanotubes. Obviously, the effective surface area of graphene materials should depend highly on the layers. Single- or few-layered graphene, with less agglomeration, should be expected to exhibit a higher effective surface area and thus better supercapacitor performance."CatalysisAs is pointed out in the review, graphene has recently received special interest in the field of catalysis because of its unique two-dimensional structure with its high surface area, special electronic and ballistic transport properties."Various graphene-based nanomaterials, such as functionalized graphenes, doped graphene, and graphene/metal or metal oxide composites, are emerging and have been investigated as catalysts for electrocatalytic reactions in fuel cells or other traditional catalytic reactions," write the authors.The paper summarizes briefly the recent progress on graphene-based materials that serve as either catalysts or catalyst supports in catalytic reactions.OutlookThe authors note that many critical problems are still waiting for efficient solutions, particularly regarding the precise structural engineering of graphene, which is crucial for both bandgap adjustment and building-block functionalization. According to them, graphene chemistry is obviously one of the best choices to solve these problems.In the meantime, graphene-based materials are emerging as highly attractive materials for real applications, especially in the area of energy conversion and storage."Since the incorporation of graphene with an active second phase, such as carbon nanotubes, conducting polymers and metal oxides, can

dramatically enhance the performance due to the synergistic effects, graphene-based composites are of scientific and industrial interest and may become competitive materials for energy-related applications," they write.Notwithstanding all the progress that has been made in the recent past, the authors conclude that the research toward an understanding of the relationship between graphene-based nanomaterials and improved performance in energy-related applications is still at its early stage, and dilemmas remain for further studies 1.

Graphene applications in electronics and photonics


"While graphene has a number of extremely useful properties, including very fast electron mobility, high mechanical strength, and excellent thermal conductivity, the interactions of graphene with its environment for example, with the substrate it is placed on, the ambient environment, or other materials in a device structure can drastically affect and change its intrinsic properties." "Our interest is to understand the properties of this new material under conditions that are present in actual technology and apply this knowledge to design, fabricate, and test graphene-based electronic and optoelectronic devices and circuits,". Unlike conventional semiconductors like silicon and gallium arsenide, which are currently used in electronics, graphene does not have a band-gap the energy difference between a material's non-conductive and conductive state. "This makes it unsuitable for building digital switches, which require the ability to switch the current off completely," However," he adds, "the excellent electrical properties of graphene, such as its high electron mobility coupled with modest current modulation, make it very appropriate for very fast (high-frequency) analog electronics," which are used in wireless communications, radar, security systems, imaging, and other applications. high-frequency graphene transistors greater than 200 gigahertz and simple electronic circuits such as frequency mixers,"and we have also demonstrated very fast photodetectors and have used them to detect optical data streams." In the future, graphene researchers need to improve the quality of synthetic graphene and to study its properties under conditions relevant to technology, who is "very optimistic" about the future of graphene in both electronics and photonics and anticipates the development of additional new applications.