Graphene Basics

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Graphene

Graphene
Graphene is a substance made of pure carbon, with atoms arranged in a regular hexagonal pattern similar to graphite, but in a one-atom thick sheet. It is an allotrope of carbon whose structure is a single planar sheet of sp2-bonded carbon atoms that are densely packed in a honeycomb crystal lattice.[1] The term graphene was coined as a combination of graphite and the suffix -ene by Hanns-Peter Boehm,[2] who described single-layer carbon foils in 1962.[3] Graphene is most easily visualized as an atomic-scale chicken wire made of carbon atoms and their bonds. The crystalline or "flake" form of graphite consists of many graphene sheets stacked together.

Graphene is an atomic-scale honeycomb lattice made of carbon atoms.

The carbon-carbon bond length in graphene is about 0.142 nanometers.[4] Graphene sheets stack to form graphite with an interplanar spacing of 0.335nm. 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 large aromatic molecule, the limiting case of the family of flat polycyclic aromatic hydrocarbons. There is an important silicon analog of graphene, called silicene. The Nobel Prize in Physics for 2010 was awarded to Andre Geim and Konstantin Novoselov at the University of Manchester "for groundbreaking experiments regarding the two-dimensional material graphene".[5]

Description
One definition given in a recent review on graphene is: 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 all other dimensionalities. It can be wrapped up into 0D fullerenes, rolled into 1D nanotubes or stacked into 3D graphite.[1] A previous definition is: A single carbon layer of the graphitic structure can be considered as the final member of the series naphthalene, anthracene, coronene, etc. and the term graphene should therefore be 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.[2] The IUPAC compendium of technology states: "previously, descriptions such as graphite layers, carbon layers, or carbon sheets have been used for the term graphene... it is incorrect to use for a single layer a term which includes the term graphite, which would imply a three-dimensional structure. The term graphene should be used only when the reactions, structural relations or other properties of individual layers are discussed."[6] In this regard, graphene has been referred to as an infinite alternant (only six-member carbon ring) polycyclic aromatic hydrocarbon (PAH). The largest known isolated molecule of this type consists of 222 atoms and is 10 benzene rings across.[7] It has proven difficult to synthesize even slightly bigger molecules, and they still remain "a dream of many organic and

Graphene polymer chemists".[8] Furthermore, ab initio calculations show that a graphene sheet is thermodynamically unstable with respect to other fullerene structures if its size is less than about 20nm (graphene is the least stable structure until about 6000 atoms) and becomes the most stable one (as within graphite) only for sizes larger than 24,000 carbon atoms.[9] The flat graphene sheet is also known to be unstable with respect to scrolling i.e. curling up, which is its lower-energy state.[10] A definition of "isolated or free-standing graphene" has also recently been proposed: "graphene is a single atomic plane of graphite, whichand this is essentialis sufficiently isolated from its environment to be considered free-standing."[11] This definition is narrower than the definitions given above and 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, for example, suspended or transferred to silicon dioxide (SiO2). A new example of isolated graphene is graphene on silicon carbide (SiC) after its passivation with hydrogen.[12]

Occurrence and production

In essence, graphene is an isolated atomic plane of graphite. From this perspective, graphene has been known since the invention of X-ray crystallography. Graphene planes become even better separated in intercalated graphite compounds. In 2004, physicists at the University of Manchester and the Institute for Microelectronics Technology, Chernogolovka, Russia, first isolated individual graphene planes by using adhesive tape.[13] They also measured electronic properties of the obtained flakes and showed their unique properties.[14] In 2005 the same Manchester Geim group together with the Philip Kim group from Columbia University (see the History section) demonstrated that quasiparticles in graphene were massless Dirac fermions. These discoveries led to an explosion of interest in graphene.

A lump of graphite, a graphene transistor and a tape dispenser. Donated to the Nobel Museum in Stockholm by Andre Geim and Konstantin Novoselov in 2010.

Since then, hundreds of researchers have entered the area, resulting in an extensive search for relevant earlier papers. The Manchester researchers themselves published the first literature review.[1] They cite several papers in which graphene or ultra-thin graphitic layers were epitaxially grown on various substrates. Also, they note a number of pre-2004 reports in which intercalated graphite compounds were studied in a transmission electron microscope. In the latter case, researchers occasionally observed extremely thin graphitic flakes ("few-layer graphene" and possibly even individual layers). An early detailed study on few-layer graphene dates back to 1962.[15] The earliest TEM images of few-layer graphene were published by G. Ruess and F. Vogt in 1948.[16] However, already D.C. Brodie was aware of the highly lamellar structure of thermally reduced graphite oxide in 1859. It was studied in detail by V. Kohlschtter and P. Haenni in 1918, who also described the properties of graphite oxide paper.[17] It is now well known that tiny fragments of graphene sheets are produced (along with quantities of other debris) whenever graphite is abraded, such as when drawing a line with a pencil.[13] There was little interest in this graphitic residue before 2004/05 and, therefore, the discovery of graphene is often attributed to Andre Geim and colleagues [18] who introduced graphene in its modern incarnation. In 2008, graphene produced by exfoliation was one of the most expensive materials on Earth, with a sample that can be placed at the cross section of a human hair costing more than $1,000 as of April 2008 (about $100,000,000/cm2).[13] Since then, exfoliation procedures have been scaled up, and now companies sell graphene in large quantities.[19] On the other hand, the price of epitaxial graphene on SiC is dominated by the substrate price, which is approximately $100/cm2 as of 2009. Even cheaper graphene has been produced by transfer from nickel by

Graphene Korean researchers,[20] with wafer sizes up to 30 inches (760mm) reported.[21] In 2011 the Institute of Electronic Materials Technology and Department of Physics, Warsaw University announced a joint development of acquisition technology of large pieces of graphene with the best quality so far.[22][23][24] In April the same year, Polish scientists with support from the Polish Ministry of Economy began the procedure for granting a patent to their discovery around the world.[25][26][27][28] In the literature, specifically that of the surface science community, graphene has also been commonly referred to as monolayer graphite. This community has intensely studied epitaxial graphene on various surfaces (over 300 articles prior to 2004). In some cases, these graphene layers are coupled to the surfaces weakly enough (by Van der Waals forces) to retain the two dimensional electronic band structure of isolated graphene,[29][30] as also happens[14] with exfoliated graphene flakes with regard to SiO2. An example of weakly coupled epitaxial graphene is the one grown on SiC (see below).

Exfoliated graphene
In 2004, the Manchester group obtained graphene by micro-mechanical alleviation of graphite. They used adhesive tape to repeatedly split graphite crystals into increasingly thinner pieces (however, filed in 2002 US Patent 6,667,100 describes the process in detail to achieve a graphite thickness of 0.01 thousands of an inch). The tape with attached optically transparent flakes was dissolved in acetone, and, after a few further steps, the flakes including monolayers were sedimented on a silicon wafer. Individual atomic planes were then hunted in an optical microscope. A year later, the researchers simplified the technique and started using dry deposition, avoiding the stage when graphene floated in a liquid. Relatively large crystallites (first, only a few micrometres in size but, eventually, larger than 1mm and visible by the naked eye) were obtained by the technique. It is often referred to as a scotch tape or drawing method. The latter name appeared because the dry deposition resembles drawing with a piece of graphite.[31] The key for the success probably was the use of high-throughput visual recognition of graphene on a properly chosen substrate, which provides a small but noticeable optical contrast. The optical properties section below contains a photograph of what graphene looks like. The isolation of graphene led to the current research boom. Previously, free-standing atomic planes were often "presumed not to exist"[14] because they are thermodynamically unstable on a nanometer scale[9] and, if unsupported, have a tendency to scroll and buckle.[8] It is currently believed that intrinsic microscopic roughening on the scale of 1nm could be important for the stability of purely 2D crystals.[32] There were a number of previous attempts to make atomically thin graphitic films by using exfoliation techniques similar to the drawing method. Multilayer samples down to 10nm in thickness were obtained. These efforts were reviewed in 2007.[1] Furthermore, a couple of very old papers were recently unearthed[15] in which researchers tried to isolate graphene starting with intercalated compounds (see History and experimental discovery). These papers reported the observation of very thin graphitic fragments (possibly monolayers) by transmission electron microscopy. Neither of the earlier observations was sufficient to "spark the graphene gold rush", until the Science paper did so by reporting not only macroscopic samples of extracted atomic planes but, importantly, their unusual properties such as the bipolar-transistor effect, ballistic transport of charges, large quantum oscillations, etc. The discovery of such interesting qualities intrinsic to graphene gave an immediate boost to further research and several groups quickly repeated the initial result and moved further. These breakthroughs also helped to attract attention to other production techniques, such as epitaxial growth of ultra-thin graphitic films. In particular, it has later been found that graphene monolayers grown on SiC and Ir are weakly coupled to these substrates (how weakly remains debated) and the graphenesubstrate interaction can be passivated further.[12] Not only graphene but also free-standing atomic planes of boron nitride, mica, dichalcogenides and complex oxides were obtained by using the drawing method.[33] Unlike graphene, the other 2D materials have so far attracted surprisingly little attention.

Graphene

Epitaxial growth on silicon carbide

Another method of obtaining graphene is to heat silicon carbide (SiC) to high temperatures (>1100 C) to reduce it to graphene.[34] This process produces epitaxial graphene with dimensions dependent upon the size of the SiC substrate (wafer). The face of the SiC used for graphene formation, silicon- or carbon-terminated, highly influences the thickness, mobility and carrier density of the graphene. Many important graphene properties have been identified in graphene produced by this method. For example, the electronic band-structure (so-called Dirac cone structure) has been first visualized in this material.[35][36][37] Weak anti-localization is observed in this material and not in exfoliated graphene produced by the pencil-trace method.[38] Extremely large, temperature-independent mobilities have been observed in SiC-epitaxial graphene. They approach those in exfoliated graphene placed on silicon oxide but still much lower than mobilities in suspended graphene produced by the drawing method. It was recently shown that even without being transferred graphene on SiC exhibits the properties of massless Dirac fermions such as the anomalous quantum Hall effect.[39][40][41][42][42] The weak van der Waals force that provides the cohesion of multilayer graphene stacks does not always affect the electronic properties of the individual graphene layers in the stack. That is, while the electronic properties of certain multilayered epitaxial graphenes are identical to that of a single graphene layer,[43] in other cases the properties are affected [35][36] as they are for graphene layers in bulk graphite. This effect is theoretically well understood and is related to the symmetry of the interlayer interactions.[43] Epitaxial graphene on SiC can be patterned using standard microelectronics methods. The possibility of large integrated electronics on SiC-epitaxial graphene was first proposed in 2004,[44] and a patent for graphene-based electronics was filed provisionally in 2003 and issued in 2006.[45] Since then, important advances have been made. In 2008, researchers at MIT Lincoln Lab produced hundreds of transistors on a single chip[46] and in 2009, very high frequency transistors were produced at the Hughes Research Laboratories on monolayer graphene on SiC.[47] Band gap of the epitaxial graphene can be tuned by irradiating with laser beams; modified graphene has a lot of advantages in device application.[48]

Epitaxial growth on metal substrates

This method uses source and the atomic structure of a metal substrate to seed the growth of the graphene (epitaxial growth). Graphene grown on ruthenium doesn't typically yield a sample with a uniform thickness of graphene layers, and bonding between the bottom graphene layer and the substrate may affect the properties of the carbon layers.[49] On the other hand, graphene grown on iridium is very weakly bonded, uniform in thickness, and can be made highly ordered. Like on many other substrates, graphene on iridium is slightly rippled. Due to the long-range order of these ripples, generation of minigaps in the electronic band-structure (Dirac cone) becomes visible.[50] High-quality sheets of few-layer graphene exceeding 1cm2 (0.2sqin) in area have been synthesized via chemical vapor deposition on thin nickel films with methane as a carbon source. These sheets have been successfully transferred to various substrates, demonstrating viability for numerous electronic applications.[21][39] An improvement of this technique has employed copper foil; at very low pressure, the growth of graphene automatically stops after a single graphene layer forms, and arbitrarily large graphene films can be created.[21][51] The aforementioned single layer growth is also due to the low concentration of carbon in methane and larger hydrocarbon gasses, such as ethane and propane, will lead to the growth of bilayer graphene.[52] In this light, it is obvious that at atmospheric-pressure CVD growth, multilayer graphene will also form on copper (similar to that grown on nickel films).[53] Growth of graphene has been demonstrated at temperatures compatible with conventional CMOS processing, using a nickel-based alloy with gold as catalysts.[54]

Graphene

Graphite oxide reduction

Graphite oxide reduction was probably historically the first method of graphene synthesis. P. Boehm reported monolayer flakes of reduced graphene oxide already in 1962.[55] In this early work existence of monolayer reduced graphene oxide flakes was demonstrated. The contribution of Boehm was recently acknowledged by Nobel prize winner for graphene research, Andre Geim: (Many Pioneers in Graphene Discovery [56]). Graphite oxide exfoliation can be achieved by rapid heating and yields highly dispersed carbon powder with a few percent of graphene flakes. Reduction of graphite oxide monolayer films e.g. by hydrazine, annealing in argon/hydrogen was reported to yield graphene films. However, the quality of graphene produced by graphite oxide reduction is lower compared to e.g. scotch-tape graphene due to incomplete removal of various functional groups by existing reduction methods. Recently, reduction and exfoliation of graphite oxide by focused solar radiation was reported with less oxygen functionalities.[57] Some spectroscopic analysis of reduced graphene oxide can be found in the literature.[58] Applying a layer of graphite oxide film to a DVD disc and burning it in a DVD writer resulted in a thin graphene film with high electrical conductivity (1738 siemens per meter) and specific surface area (1520 square meters per gram), besides being highly resistant and malleable.[59][60]

Growth from metal-carbon melts

The general idea in this process is to dissolve carbon atoms inside a transition metal melt at a certain temperature, and then allow the dissolved carbon to precipitate out at lower temperatures as single layer graphene (SLG).[61] The metal is first melted in contact with a carbon source. This source could be the graphite crucible inside which the melting process is carried out or it could be the graphite powder or chunk sources which are simply placed in contact with the melt. Keeping the melt in contact with carbon source at a given temperature will give rise to dissolution and saturation of carbon atoms in the melt based on the binary phase diagram of metal-carbon. Upon lowering the temperature, solubility of the carbon in the molten metal will decrease and the excess amount of carbon will precipitate on top of the melt. The floating layer can be either skimmed or allowed to freeze for removal afterwards. Different morphology including thick graphite, few layer graphene (FLG) and SLG were observed on metal substrate. The Raman spectroscopy proved that SLG has been successfully grown on nickel substrate. The SLG Raman spectrum featured no D and D' band, indicating the pristine and high-quality nature of SLG. Among transition metals, nickel provides a better substrate for growing SLG. Since nickel is not Raman active, the direct Raman spectroscopy of graphene layers on top of the nickel is achievable. The graphene-metal composite could be utilized in thermal interface materials for thermal management applications.[61]

Pyrolysis of sodium ethoxide

A 2008 publication described a process for producing gram-quantities of graphene, by the reduction of ethanol by sodium metal, followed by pyrolysis of the ethoxide product, and washing with water to remove sodium salts.[62]

From nanotubes
Experimental methods for the production of graphene ribbons are reported consisting of cutting open nanotubes.[63] In one such method multi-walled carbon nanotubes are cut open in solution by action of potassium permanganate and sulfuric acid.[64] In another method graphene nanoribbons are produced by plasma etching of nanotubes partly embedded in a polymer film.[65]

Graphene

From graphite by sonication

It consists in dispersing graphite in a proper liquid medium that is then sonicated. Non exfoliated graphite is eventually separated from graphene by centrifugation. This method was first proposed by Hernandez et al.[66] who obtained graphene concentration up to 0.01mg/ml in N-methylpyrrolidone (NMP). The method was then largely improved by several groups. In particular, it was greatly developed by the Italian group of Alberto Mariani. Mariani et al. reached the concentration of 2.1mg/ml in NMP (the highest in this solvent).[67] The same group published the highest graphene concentrations reported so far in any liquid and obtained by any method. An example is the use of a suitable ionic liquid as the dispersing liquid medium for graphite exfoliation;[68] in this medium the very high concentration of 5.33mg/ml was obtained.

Carbon dioxide reduction method

Graphene Technologies, a dba of High Temperature Physics LLC, has discovered and developed a novel process for scalable production of single to few layer graphene employing an exothermic combustion reaction of certain Group I and II metals, including magnesium, and carbon bearing gases, including carbon dioxide. The first two of a series of patent applications by High Temperature Physics, have been published. The graphene powder created by the GT process is uniquely small and high purity. Narayan Hosmane and co-workers at Northern Illinois University in the United States subsequently published a paper on this method involving a common experiment. The team showed that graphene was formed in few-layer nanosheets up to 10 atoms thick. The material was characterized by Raman spectroscopy, energy-dispersive X-ray analysis, X-ray powder diffraction, and transmission electron microscopy.[69]

Properties
Atomic structure
The atomic structure of isolated, single-layer graphene was studied by transmission electron microscopy (TEM) on sheets of graphene suspended between bars of a metallic grid.[32] Electron diffraction patterns showed the expected hexagonal lattice of graphene. Suspended graphene also showed "rippling" of the flat sheet, with amplitude of about one nanometer. These ripples may be intrinsic to graphene as a result of the instability of two-dimensional crystals,[1][70][71] or may be extrinsic, originating from the ubiquitous dirt seen in all TEM images of graphene. Atomic resolution real-space images of isolated, single-layer graphene on SiO2 substrates were obtained[72][73] by scanning tunneling microscopy. Graphene processed using lithographic techniques is covered by photoresist residue, which must be cleaned to obtain atomic-resolution images.[72] Such residue may be the "adsorbates" observed in TEM images, and may explain the rippling of suspended graphene. Rippling of graphene on the SiO2 surface was determined to be caused by conformation of graphene to the underlying SiO2, and not an intrinsic effect.[72] Graphene sheets in solid form (density > 1 g/cm3) usually show evidence in diffraction for graphite's 0.34nm (002) layering. This is true even of some single-walled carbon nanostructures.[74] However, unlayered graphene with only (hk0) rings has been found in the core of presolar graphite onions.[75] Transmission electron microscope studies show faceting at defects in flat graphene sheets,[76] and suggest a possible role in this unlayered-graphene for two-dimensional crystallization from a melt. A University of Manchester study, published in the journal Mesoscale and Nanoscale Physics,[77] shows that graphene can self-repair holes in graphene sheets, when exposed to molecules containing carbon, like hydrocarbons. When bombarded with pure carbon atoms, the holes in graphene sheets are completely filled, with carbon atom snapping to the gaps and perfectly aligning into hexagon shapes.[78]

Graphene

Electronic properties
Graphene differs from most conventional three-dimensional materials. Intrinsic graphene is a semi-metal or zero-gap semiconductor. Understanding the electronic structure of graphene is the starting point for finding the band structure of graphite. It was realized as early as 1947 by P. R. Wallace[79] that the E-k relation is linear for low energies near the six corners of the two-dimensional hexagonal Brillouin zone, leading to zero effective mass for electrons and holes. [80] Due to this linear (or conical") dispersion relation at low energies, electrons and holes near these six points, two of which are inequivalent, behave like relativistic particles described by the Dirac equation for spin 1/2 particles.[81][82] Hence, the electrons and holes are called Dirac fermions also called Graphinos,[83] and the six corners of the Brillouin zone are called the Dirac points.[81] The equation describing the E-k relation is ; where the Fermi velocity vF ~ 106 m/s.[82]

GNR band structure for zig-zag orientation. Tightbinding calculations show that zigzag orientation is always metallic.

Electronic transport Experimental results from transport measurements show that graphene has a remarkably high electron mobility at GNR band structure for arm-chair orientation. Tightbinding calculations show that armchair orientation can be semiconducting or metallic depending on width (chirality). room temperature, with reported values in excess of 15,000 cm2V1s1.[1] Additionally, the symmetry of the experimentally measured conductance indicates that the mobilities for holes and electrons should be nearly the same.[80] The mobility is nearly independent of temperature between 10 K and 100 K,[84][85][86] which implies that the dominant scattering mechanism is defect scattering. Scattering by the acoustic phonons of graphene places intrinsic limits on the room temperature mobility to 200,000 cm2V1s1 at a carrier density of 1012 cm2.[86][87] The corresponding resistivity of the graphene sheet would be 106 cm. This is less than the resistivity of silver, the lowest resistivity substance known at room temperature.[88] However, for graphene on SiO2 substrates, scattering of electrons by optical phonons of the substrate is a larger effect at room temperature than scattering by graphenes own phonons. This limits the mobility to 40,000 cm2 V1s1.[86]

Graphene Despite the zero carrier density near the Dirac points, graphene exhibits a minimum conductivity on the order of . The origin of this minimum conductivity is still unclear. However, rippling of the graphene sheet or ionized impurities in the SiO2 substrate may lead to local puddles of carriers that allow conduction.[80] Several theories suggest that the minimum conductivity should be ; however, most measurements are of order or greater[1] and depend on impurity concentration.[89] Recent experiments have probed the influence of chemical dopants on the carrier mobility in graphene.[89][90] Schedin et al. doped graphene with various gaseous species (some acceptors, some donors), and found the initial undoped state of a graphene structure can be recovered by gently heating the graphene in vacuum. They reported that even for chemical dopant concentrations in excess of 1012 cm2 there is no observable change in the carrier mobility.[90] Chen, et al. doped graphene with potassium in ultra high vacuum at low temperature. They found that potassium ions act as expected for charged impurities in graphene,[91] and can reduce the mobility 20-fold.[89] The mobility reduction is reversible on heating the graphene to remove the potassium. Due to its two-dimensional property, charge fractionalization (where the apparent charge of individual pseudoparticles in low-dimensional systems is less than a single quantum[92]) is thought to occur in graphene. It may therefore be a suitable material for the construction of quantum computers using anyonic circuits.[93][94]

Optical properties
Graphene's unique optical properties produce an unexpectedly high opacity for an atomic monolayer, with a startlingly simple value: it absorbs 2.3% of white light, where is the fine-structure constant.[95] This is "a consequence of the unusual low-energy electronic structure of monolayer graphene that features electron and hole conical bands meeting each other at the Dirac point... [which] is qualitatively different from more common quadratic massive bands".[96] Based on the Slonczewski-Weiss-McClure (SWMcC) band model of graphite, the interatomic distance, hopping value and frequency cancel when the optical conductance is calculated using the Fresnel equations in the thin-film limit. This has been confirmed experimentally, but the measurement is not precise enough to improve on other techniques for determining the fine-structure constant.[97]

Photograph of graphene in transmitted light. This one-atom-thick crystal can be seen with the naked eye because it absorbs approximately 2.3% of white light.

The band gap of graphene can be tuned from 0 to 0.25 eV (about 5 micrometre wavelength) by applying voltage to a dual-gate bilayer graphene field-effect transistor (FET) at room temperature.[98] The optical response of graphene nanoribbons has also been shown to be tunable into the terahertz regime by an applied magnetic field.[99] It has been shown that graphene/graphene oxide system exhibits electrochromic behavior, allowing tuning of both linear and ultrafast optical properties.[100] Saturable absorption It is further confirmed that such unique absorption could become saturated when the input optical intensity is above a threshold value. This nonlinear optical behavior is termed saturable absorption and the threshold value is called the saturation fluence. Graphene can be saturated readily under strong excitation over the visible to near-infrared region, due to the universal optical absorption and zero band gap. This has relevance for the mode locking of fiber lasers, where fullband mode locking has been achieved by graphene-based saturable absorber. Due to this special property,

Graphene graphene has wide application in ultrafast photonics. Moreover, the ultrafast optical response of graphene/graphene oxide layers can be tuned electrically.[100] [101] [102] Furthermore, Saturable absorption in graphene could occur at the Microwave and Terahertz band, owing to its wideband optical absorption property. The microwave saturable absorption in graphene demonstrates that graphene microwave and Terahertz photonics devices could emerge, such as: microwave saturable absorber, modulator, polarizer,microwave signal processing,and broad-band wireless access networks [103] Nonlinear Kerr effect Under more intensive laser illumination, graphene could also possess a nonlinear phase shift due to the optical nonlinear Kerr effect, besides the well-known saturable absorption property. Based on a typical open and close aperture z-scan measurement, graphene is found to possess a giant non-linear Kerr coefficient of 107 cm2W1 almost nine orders of magnitude larger than that of bulk dielectrics [104]. This suggests that graphene may be a very promising nonlinear Kerr medium, paving the way for graphene-based nonlinear Kerr photonics such as soliton in graphene.

Excitonic properties
First-principle calculations with quasiparticle corrections and many body effects are performed to study the electronic and optical properties of graphene-based materials. The approach is described as three stages.[105] With GW calculation, the properties of graphene-based materials are accurately investigated, including graphene,[106] graphene nanoribbons,[107][108][109] edge and surface functionalized armchair graphene nanoribbons,[110] hydrogen saturated armchair graphene nanoribbons,[111] Josephson effect in graphene SNS junctions with single localized defect,[112][113] and scaling properties in armchair graphene nanoribbons.[114]

Spin transport
Graphene is thought to be an ideal material for spintronics due to small spin-orbit interaction and near absence of nuclear magnetic moments in carbon. Electrical spin-current injection and detection in graphene was recently demonstrated up to room temperature.[115][116][117] Spin coherence length above 1 micrometre at room temperature was observed,[115] and control of the spin current polarity with an electrical gate was observed at low temperature.[116]

Anomalous quantum Hall effect

The quantum Hall effect is relevant for accurate measuring standards of electrical quantities, and in 1985 Klaus von Klitzing received the Nobel prize for its discovery. The effect concerns the dependence of a transverse conductivity on a magnetic field, which is perpendicular to a current-carrying stripe. Usually the phenomenon, the quantization of the so-called Hall conductivity at integer multiples of the basic quantity (where e is the elementary electric charge and h is Planck's constant) can be observed only in very clean Si or GaAs solids, and at very low temperatures around 3K, and at very high magnetic fields. Graphene in contrast, besides its high mobility and minimum conductivity, and because of certain peculiarities explained in Pseudo-relativistic theory below, shows particularly interesting behavior just in the presence of a magnetic field and just with respect to the conductivity-quantization: it displays an anomalous quantum Hall effect with the sequence of steps shifted by 1/2 with respect to the standard sequence, and with an additional factor of 4. Thus, in graphene the Hall conductivity is , where N is the above-mentioned integer "Landau level" index, and the double valley and double spin degeneracies give the factor of 4.[1] Moreover, in graphene these remarkable anomalies can even be measured at room temperature, i.e. at roughly 20C.[84] This anomalous behavior is a direct result of the emergent massless Dirac electrons in graphene. In a magnetic field, their spectrum has a Landau level with energy precisely at the Dirac point. This level is a consequence of the

Graphene Atiyah-Singer index theorem and is half-filled in neutral graphene,[81] leading to the "+1/2" in the Hall conductivity.[118] Bilayer graphene also shows the quantum Hall effect, but with the standard sequence (with with only one of the two anomalies. Interestingly, concerning the second anomaly, the first plateau at N = 0 is absent, indicating that bilayer graphene stays metallic at the neutrality point.[1] Unlike normal metals, the longitudinal resistance of graphene shows maxima rather than minima for integral values of the Landau filling factor in measurements of the ShubnikovDe Haas oscillations, which show a phase shift of , known as Berrys phase.[80][84] The Berrys phase arises due to the zero effective carrier mass near the Dirac points.[119] Study of the temperature dependence of the Shubnikov-de Haas oscillations in graphene reveals that the carriers have a non-zero cyclotron mass, despite their zero effective mass from the E-k relation.[84]

10

Anomalous quantum Hall effect in strong magnetic fields

The quantum Hall effect in graphene in sufficiently strong magnetic fields (above 10 Teslas or so) reveals additional interesting features. Additional plateaus of the Hall conductivity at with are observed.[120] Also, the observation of a plateau at were reported. These observations of the quantum Hall effect with
[121][122] [121]

and the fractional quantum Hall effect at indicate that the four-fold degeneracy

(two valley and two spin degrees of freedom) of the Landau energy levels is partially or completely lifted. According to one of the suggestions, it is the magnetic catalysis of symmetry breaking that is responsible for lifting the degeneracy of the Landau levels.

Nanostripes
Nanostripes of graphene (in the "zig-zag" orientation), at low temperatures, show spin-polarized metallic edge currents, which also suggests applications in the new field of spintronics. (In the "armchair" orientation, the edges behave like semiconductors.[123])

Graphene oxide
By dispersing oxidized and chemically processed graphite in water, and using paper-making techniques, the monolayer flakes form a single sheet and bond very powerfully. These sheets, called graphene oxide paper have a measured tensile modulus of 32 GPa.[124] The peculiar chemical property of graphite oxide is related to the functional groups attached to graphene sheets. They even can significantly change the pathway of polymerization and similar chemical processes.[125] Graphene Oxide flakes in polymers also shown enhanced photo-conducting properties.[126] A team at Manchester University led by Andre Geim published findings showing that graphene-based membranes are impermeable to all gases and liquids (vacuum-tight). However, water evaporates through them as quickly as if the membranes were not there at all.[127]

Chemical modification
Soluble fragments of graphene can be prepared in the laboratory[128] through chemical modification of graphite. First, microcrystalline graphite is treated with a strongly acidic mixture of sulfuric acid and nitric acid. A series of steps involving oxidation and

Photograph of single-layer graphene oxide undergoing high temperature chemical treatment, resulting in sheet folding and loss of carboxylic functionality, or through room temperature carbodiimide treatment, collapsing into star-like clusters.

Graphene exfoliation result in small graphene plates with carboxyl groups at their edges. These are converted to acid chloride groups by treatment with thionyl chloride; next, they are converted to the corresponding graphene amide via treatment with octadecylamine. The resulting material (circular graphene layers of 5.3 angstrom thickness) is soluble in tetrahydrofuran, tetrachloromethane and dichloroethane. Refluxing single-layer graphene oxide (SLGO) in solvents leads to size reduction and folding of the individual sheets as well as loss of carboxylic group functionality, by up to 20%, indicating thermal instabilities of SLGO sheets dependant on their preparation methodology. When using thionyl chloride, acyl chloride groups result, which can then form aliphatic and aromatic amides with a reactivity conversion of around 70-80%. Hydrazine reflux is commonly used for reducing SLGO to SLG(R), but titrations show that only around 20-30% of the carboxylic groups are lost leaving a significant number of COOH groups available for chemical attachment. Analysis of SLG(R) generated by this route reveals that the system is unstable and using a room temperature stirring with HCl (< 1.0 M) leads to around 60% loss of COOH functionality. Room temperature Boehm titration results for various chemical reactions of single-layer graphene oxide, which reveal reactivity of the carboxylic groups and the resultant stability of the SLGO treatment of SLGO with carbodiimides sheets after treatment. leads to the collapse of the individual sheets into star-like clusters, which exhibited poor subsequent reactivity with amines (ca. 3-5% conversion of the intermediate to the final amide).[129] It is apparent that conventional chemical treatment of carboxylic groups on SLGO generates morphological changes of individual sheets that leads to a reduction in chemical reactivity, which may potentially limit their use in composite synthesis. Therefore, other types of chemical reactions have been explored. SLGO has also been grafted with polyallylamine, cross-linked through epoxy groups. When filtered into graphene oxide paper, these composites exhibit sheets increased stiffness and strength relative to unmodified graphene oxide paper.[130] Full hydrogenation from both sides of graphene sheet results in graphane, but partial hydrogenation leads to hydrogenated graphene[131]

11

Thermal properties
The near-room temperature thermal conductivity of graphene was measured to be between (4.840.44) 103 to (5.300.48) 103 Wm1K1. These measurements, made by a non-contact optical technique, are in excess of those measured for carbon nanotubes or diamond. The isotopic composition, the ratio of 12C to 13C, has a significant impact on thermal conductivity, where isotopically pure 12C graphene has higher conductivity than either a 50:50 isotope ratio or the naturally occurring 99:1 ratio.[132] It can be shown by using the Wiedemann-Franz law, that the thermal conduction is phonon-dominated.[133] However, for a gated graphene strip, an applied gate bias causing a Fermi energy shift much larger than kBT can cause the electronic contribution to increase and dominate over the phonon contribution at low temperatures. The ballistic thermal conductance of graphene is isotropic.[134][135] Potential for this high conductivity can be seen by considering graphite, a 3D version of graphene that has basal plane thermal conductivity of over a 1000 Wm1K1 (comparable to diamond). In graphite, the c-axis (out of plane) thermal conductivity is over a factor of ~100 smaller due to the weak binding forces between basal planes as well as the larger lattice spacing.[136] In addition, the ballistic thermal conductance of a graphene is shown to give the lower limit of the ballistic thermal conductances, per unit circumference, length of carbon nanotubes.[137]

Graphene Despite its 2-D nature, graphene has 3 acoustic phonon modes. The two in-plane modes (LA, TA) have a linear dispersion relation, whereas the out of plane mode (ZA) has a quadratic dispersion relation. Due to this, the T2 dependent thermal conductivity contribution of the linear modes is dominated at low temperatures by the T1.5 contribution of the out of plane mode.[137] Some graphene phonon bands display negative Grneisen parameters.[138] At low temperatures (where most optical modes with positive Grneisen parameters are still not excited) the contribution from the negative Grneisen parameters will be dominant and thermal expansion coefficient (which is directly proportional to Grneisen parameters) negative. The lowest negative Grneisen parameters correspond to the lowest transversal acoustic ZA modes. Phonon frequencies for such modes increase with the in-plane lattice parameter since atoms in the layer upon stretching will be less free to move in the z direction. This is similar to the behavior of a string which is being stretched will have vibrations of smaller amplitude and higher frequency. This phenomenon, named "membrane effect", was predicted by Lifshitz in 1952.[139]

12

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 greater than steel, with a tensile modulus (stiffness) of 1 TPa (150,000,000 psi).[140] However, the process of separating it from graphite, where it occurs naturally, will require some technological development before it is economical enough to be used in industrial processes,[141] though this may be changing soon.[142] Aside from being very strong, graphene is very light, weighing only about 0.77 milligrams per square meter. The Nobel announcement illustrated this by saying that a 1 square meter graphene hammock would support a 4 kg cat but would weigh only as much as one of the cat's whiskers[143]. Graphene paper or GP has recently been developed by a research department from the University of Technology Sydney by Guoxiu Wang, that can be processed, reshaped and reformed from its original raw material state. Researchers have successfully milled the raw graphite by purifying and filtering it with chemicals to reshape and reform it into nano-structured configurations which are then processed into sheets as thin as paper, according to a university statement. Lead researcher Ali Reza Ranjbartoreh said: 'Not only is it lighter, stronger, harder and more flexible than steel, it is also a recyclable and sustainably manufacturable product that is eco-friendly and cost effective in its use.' Ranjbartoreh said the results would allow the development of lighter and stronger cars and planes that use less fuel, generate less pollution, are cheaper to run and ecologically sustainable. He said large aerospace companies have already started to replace metals with carbon fibres and carbon-based materials, and graphene paper with its incomparable mechanical properties would be the next material for them to explore. Using an atomic force microscope (AFM), the spring constant of suspended graphene sheets has been measured. Graphene sheets, held together by van der Waals forces, were suspended over SiO2 cavities where an AFM tip was probed to test its mechanical properties. Its spring constant was in the range 15 N/m and the Young's modulus was 0.5 TPa, which differs from that of the bulk graphite. These high values make graphene very strong and rigid. These intrinsic properties could lead to using graphene for NEMS applications such as pressure sensors and resonators.[144] As is true of all materials, regions of graphene are subject to thermal and quantum fluctuations in relative displacement. Although the amplitude of these fluctuations is bounded in 3D structures (even in the limit of infinite size), the Mermin-Wagner theorem shows that the amplitude of long-wavelength fluctuations will grow logarithmically with the scale of a 2D structure, and would therefore be unbounded in structures of infinite size. Local deformation and elastic strain are negligibly affected by this long-range divergence in relative displacement. It is believed that a sufficiently large 2D structure, in the absence of applied lateral tension, will bend and crumple to form a fluctuating 3D structure. Researchers have observed ripples in suspended layers of graphene,[32] and it has been proposed that the ripples are caused by thermal fluctuations in the material. As a consequence of these dynamical deformations, it is debatable whether graphene is truly a 2D structure.[1][70][71][145][146]

Graphene

13

Casimir effect
The Casimir effect is an interaction between any disjoint neutral bodies provoked by the fluctuations of the electrodynamical vacuum. Mathematically it can be explained by considering the normal modes of electromagnetic field which explicitly depend on the boundary (or matching) conditions on the surfaces of the interacting bodies. Since the interaction of graphene with electromagnetic field is surprisingly strong for a one-atom-thick material, the Casimir effect in the graphene systems is of growing research interest.[147][148]

Bilayer graphene
Bilayer graphene is two layers of graphene and it has been shown to have interesting electrical properties, such as the quantum hall effect, a tunable band gap,[149] and potential for excitonic condensation[150]making them promising candidates for optoelectronic and nanoelectronic applications. Bilayer graphene typically can be found either in twisted configurations where two layer are rotated relative to each other or a graphitic Bernal stacked configurations where half the atoms in one layer lie atop half the atoms in the other. Stacking order and orientation greatly influence the optical and electronic properties of bilayer graphene. One way to synthesize bilayer graphene is via chemical vapor deposition, and can produce large area bilayer regions that almost exclusively conform to a Bernal stack geometry.[151]

Potential applications
Several potential applications for graphene are under development, and many more have been proposed. These include lightweight, thin, flexible, yet durable display screens, electric circuits, and solar cells, as well as various medical, chemical, and industrial processes enhanced or enabled by the use of new graphene materials.

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 field-effect transistor. 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 (mechanical exfoliation on SiO2 / Si or thermal graphitization of a SiC surface) onto a target substrate of interest.[152] In 2008, the smallest transistor so far, one atom thick, 10 atoms wide was made of graphene.[153] IBM announced in December 2008 that they fabricated and characterized graphene transistors operating at GHz frequencies.[154] In May 2009, an n-type transistor was announced meaning that both n and p-type transistors have now been created with graphene.[155] A functional graphene integrated circuit was also demonstrated a complementary inverter consisting of one p- and one n-type graphene transistor.[156] However, this inverter also suffered from a very low voltage gain. According to a January 2010 report,[157] graphene was epitaxially grown on SiC in a quantity and with quality suitable for mass production of integrated circuits. At high temperatures, the Quantum Hall effect could be measured in these samples. See also the 2010 work by IBM in the transistor section above in which 'processors' of fast transistors on 2-inch (51mm) graphene sheets were made.[158][159] In June 2011, IBM researchers announced that they had succeeded in creating the first graphene-based integrated circuit, a broadband radio mixer.[160] The circuit handled frequencies up to 10GHz, and its performance was unaffected by temperatures up to 127 degrees Celsius.

Graphene

14

Electrochromic devices
Graphene oxide can be reversibly reduced and oxidized using electrical stimulus. Controlled reduction and oxidation in two-terminal devices containing multilayer graphene oxide films are shown to result in switching between partially reduced graphene oxide and graphene, a process which modifies the electronic and optical properties. Oxidation and reduction are also shown to be related to resistive switching. [161] [162]

Transparent conducting electrodes

Graphene's high electrical conductivity and high optical transparency make it a candidate for transparent conducting electrodes, required for such applications as touchscreens, liquid crystal displays, organic photovoltaic cells, and organic light-emitting diodes. In particular, graphene's mechanical strength and flexibility are advantageous compared to indium tin oxide, which is brittle, and graphene films may be deposited from solution over large areas.[163][164] Large-area, continuous, transparent, and highly conducting few-layered graphene lms were produced by chemical vapor deposition and used as anodes for application in photovoltaic devices. A power conversion efficiency (PCE) up to 1.71% was demonstrated, which is 55.2% of the PCE of a control device based on indium-tin-oxide.[165] Organic light-emitting diodes (OLEDs) with graphene anodes have also been demonstrated.[166] The electronic and optical performance of devices based on graphene are shown to be similar to devices made with indium-tin-oxide. An all carbon-based device called a light-emitting electrochemical cell (LEC) was demonstrated with chemically derived graphene as the cathode and the conductive polymer PEDOT as the anode by Matyba et al.[167] Unlike its predecessors, this device contains no metal, but only carbon-based electrodes. The use of graphene as the anode in LECs was also verified in the same publication.

Room temperature distillation of ethanol for fuel and human consumption

Graphene oxide membranes will allow water vapor to pass through, but have been shown to be impermeable to all other liquids and gases including helium .[127] This phenomenon has been used for further distilling of vodka to higher alcohol concentrations, in a room-temperature laboratory, without the application of heat or vacuum normally used in traditional distillation methods.[168] Further development and commercialization of such membranes could revolutionize the economics of biofuel production and the alcoholic beverage industry.

Desalination
Research suggests that graphene filters could outperform other techniques of desalination by a significant margin.[169][170]

Solar cells
The USC Viterbi School of Engineering lab reported the large scale production of highly transparent graphene films by chemical vapor deposition in 2008. In this process, researchers create ultra-thin graphene sheets by first depositing carbon atoms in the form of graphene films on a nickel plate from methane gas. Then they lay down a protective layer of thermoplastic over the graphene layer and dissolve the nickel underneath in an acid bath. In the final step they attach the plastic-protected graphene to a very flexible polymer sheet, which can then be incorporated into an OPV cell (graphene photovoltaics). Graphene/polymer sheets have been produced that range in size up to 150 square centimeters and can be used to create dense arrays of flexible OPV cells. It may eventually be possible to run printing presses laying extensive areas covered with inexpensive solar cells, much like newspaper presses print newspapers (roll-to-roll).[171][172]

Graphene

15

Single-molecule gas detection

Theoretically 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. However, similar to carbon nanotubes, graphene has no dangling bonds on its surface. Gaseous molecules cannot be readily adsorbed onto graphene surface. So intrinsically graphene is insensitive.[173] The sensitivity of graphene chemical gas sensors can be dramatically enhanced by functionalizing graphene, for example, coating with a thin layer of certain polymers. The thin polymer layer acts like a concentrator that absorbs gaseous molecules. The molecule absorption introduces a local change in electrical resistance of graphene sensors. 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.[90]

Graphene nanoribbons
Graphene nanoribbons (GNRs) are essentially single layers of graphene that are cut in a particular pattern to give them 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 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 width.[174] Indeed, experimental results show that the energy gaps do increase with decreasing GNR width.[175] 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.[176] Large quantities of width controlled GNRs can be produced via graphite nanotomy process.[177]

Graphene quantum dots

Graphene quantum dots (GQDs) are single atom thick sheets of graphene with all dimensions less than 100nm. Their size and edge crystallography govern their electrical, magnetic, optical and chemical properties. GQDs can be produced via graphite nanotomy as shown by Berry group [177] or via bottom-up, solution-based routes (Diels-Alder, cyclotrimerization and/or cyclodehydrogenation reactions) shown by Mullen group.[178] Several studies[153] have indicated that GQDs with controlled structure can be incorporated into a wide variety of applications in electronics, optoelectronics and electromagnetics.

Graphene transistors
Due to its high electronic quality, graphene has also attracted the interest of technologists who see it 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). In their 2004 paper,[14] the Manchester group demonstrated FETs with a "rather modest" on-off ratio of ~30 at room temperature. In 2006, Georgia Tech researchers, led by Walter de Heer, announced that they had successfully built an all-graphene planar FET with side gates.[179] Their devices showed changes of 2% at cryogenic temperatures. The first top-gated FET (on-off ratio of <2) was demonstrated by researchers of AMICA and RWTH Aachen University in 2007.[180] Graphene nanoribbons may prove generally capable of replacing silicon as a semiconductor in modern technology.[181] Facing 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 AMICA and 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

Graphene applied to nonvolatile memories.[182] In 2009, researchers at the Politecnico di Milano demonstrated four different types of logic gates, each composed of a single graphene transistor.[183] In the same year, the Massachusetts Institute of Technology researchers built an experimental graphene chip 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 that frequency.[184] Similar results are obtained in.[185] 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 demonstrated to operate at frequencies higher than 25kHz. In the same year, tight-binding numerical simulations [186] obtained by means of the open-source software NanoTCAD ViDES [187] have demonstrated that the band-gap induced in graphene bilayer field effect transistors is not sufficiently large for high-performance transistors for digital applications, but it can be sufficient for ultra-low voltage applications, when exploiting a tunnel-FET architecture.[188] In February 2010, researchers at IBM reported that they have been able to create graphene transistors with an on and off rate of 100 gigahertz, far exceeding the rates of previous attempts, and exceeding the speed of silicon transistors with an equal gate length. The 240nm graphene transistors made at IBM were made using extant silicon-manufacturing equipment, meaning that for the first time graphene transistors are a conceivablethough still fancifulreplacement for silicon.[158] [159] [189] In November 2011, researchers at Cambridge University demonstrated the feasibility of ink-jet printing as a method for fabricating graphene devices.[190]

16

Graphene optical modulators

When the Fermi level of graphene is tuned, the optical absorption of graphene can be changed. In 2011, researchers at UC Berkeley reported the first graphene-based optical modulator. Operating at 1.2GHz without any temperature controller, this modulator has a broad bandwidth (from 1.3 to 1.6 m) and small footprint (~25 m2).[191]

Reference material for characterizing electroconductive and transparent materials

One layer of graphene absorbs 2.3% of white light.[192] This property was used to define the Conductivity of Transparency that combines the sheet resistance and the transparency. This parameter was used to compare different materials without the use of two independent parameters.[193]

Thermal management materials

In 2011, researchers in Georgia Institute of Technology reported that a three-dimensional vertically aligned functionalized multilayer graphene architecture can be an approach for graphene-based thermal interfacial materials (TIMs) with superior equivalent thermal conductivity and ultra-low interfacial thermal resistance between graphene and metal.[135]

Ultracapacitors
Due to the extremely high surface area to mass ratio of graphene, one potential application is in the conductive plates of ultracapacitors. It is believed that graphene could be used to produce ultracapacitors with a greater energy storage density than is currently available.[194]

Graphene

17

Engineered piezoelectricity
Density functional theory simulations predict that depositing certain adatoms on graphene can render it piezoelectrically responsive to an electric field applied in the vertical (i.e. out-of-plane) direction. This type of locally engineered piezoelectricity is similar in magnitude to that of bulk piezoelectric materials and make graphene a candidate tool for control and sensing in nanoscale devices.[195][196]

Graphene biodevices
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.[197] The most ambitious biological application of graphene is for rapid, inexpensive electronic DNA sequencing. Integration of graphene (thickness of 0.34nm) layers as nanoelectrodes into a nanopore[198] can solve one of the bottleneck issues of nanopore-based single-molecule DNA sequencing.

Anti-bacterial
The Chinese Academy of Sciences has found that sheets of graphene oxide are highly effective at 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 periods of time.[199]

Pseudo-relativistic theory
The electrical properties of graphene can be described by a conventional tight-binding model; in this model the energy of the electrons with wave vector k is[79][81]
Energy of the electrons with wavenumber k in graphene, calculated in the Tight Binding-approximation. The unoccupied (occupied) states, colored in blue-red (yellow-green), touch each other without energy gap exactly at the above-mentioned six k-vectors.

with the nearest-neighbor hopping energy 0 2.8 eV and the lattice constant a 2.46 . Conduction and valence band, respectively, correspond to the different signs in the above dispersion relation; they touch each other in six points, the "K-values". However, only two of these six points are independent, whereas the rest is equivalent by symmetry. In the vicinity of the K-points the energy depends linearly on the wave vector, similar to a relativistic particle. Since an elementary cell of the lattice has a basis of two atoms, the wave function even has an effective 2-spinor structure. As a consequence, at low energies, even neglecting the true spin, the electrons can be described by an equation which is formally equivalent to the massless Dirac equation. Moreover, in the present case this pseudo-relativistic description is restricted to the chiral limit, i.e., to vanishing rest mass M0, which leads to interesting additional features:[81][200]

Here vF ~ 106 is the Fermi velocity in graphene which replaces the velocity of light in the Dirac theory; vector of the Pauli matrices, is the two-component wave function of the electrons, and E is their energy.

is the
[123]

Graphene

18

History and experimental discovery

The term graphene first appeared in 1987[201] 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 intercalant and graphene. The term was also used in early descriptions of carbon nanotubes,[202] as well as for epitaxial graphene,[203] and polycyclic aromatic hydrocarbons.[204] Larger graphene molecules or sheets (so that they can be considered as true isolated 2D crystals) cannot be grown even in principle. An article in Physics Today reads: Fundamental forces place seemingly insurmountable barriers in the way of creating [2D crystals]... The nascent 2D crystallites try to minimize their surface energy and inevitably morph into one of the rich variety of stable 3D structures that occur in soot. But there is a way around the problem. Interactions with 3D structures stabilize 2D crystals during growth. So one can make 2D crystals sandwiched between or placed on top of the atomic planes of a bulk crystal. In that respect, graphene already exists within graphite... One can then hope to fool Nature and extract single-atom-thick crystallites at a low enough temperature that they remain in the quenched state prescribed by the original higher-temperature 3D growth.[31] Single layers of graphite were previously (starting from the 1970s) grown epitaxially on top of other materials.[205] This "epitaxial graphene" consists of a single-atom-thick hexagonal lattice of sp2-bonded carbon atoms, as in free-standing graphene. However, there is significant charge transfer from the substrate to the epitaxial graphene, and, in some cases, hybridization between the d orbitals of the substrate atoms and orbitals of graphene, which significantly alters the electronic structure of the epitaxial graphene. Single layers of graphite were also observed by transmission electron microscopy within bulk materials (see section Occurrence), in particular inside soot obtained by chemical exfoliation.[13] 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)[13] 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-atom-thick crystallites (graphene) from bulk graphite in 2004.[14] 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 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.

Andre Geim and Konstantin Novoselov, 2010

The micromechanical cleavage technique led directly to the first observation of the anomalous quantum Hall effect in graphene,[84][119] which provided direct evidence of the theoretically predicted pi Berry's phase of massless Dirac fermions in graphene. The anomalous quantum Hall effect in graphene was reported around the same time by Geim and Novoselov and by Philip Kim and Yuanbo Zhang in 2005. These simple experiments started after the researchers watched colleagues who were looking for quantum Hall effect [206] and Dirac fermions [207] in bulk graphite. 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 Krber Prize for "develop[ing]

Graphene the first two-dimensional crystals made of carbon atoms". In 2008 and 2009, Reuters (which also runs a bibliometric service Web of Science) tipped him as one of the front-runners for a Nobel prize in Physics.[208] On October 5, 2010, the Nobel Prize in Physics for the year was awarded to Andre Geim and Konstantin Novoselov from the University of Manchester for their work on graphene.[209] The theory of graphene was first explored by P. R. Wallace in 1947 as a starting point for understanding the electronic properties of more complex, 3D graphite. The emergent massless Dirac equation was first pointed out by Gordon Walter Semenoff and David P. DeVincenzo and Eugene J. Mele.[210] Semenoff emphasized the occurrence in a magnetic field of an electronic Landau level precisely at the Dirac point. This level is responsible for the anomalous integer quantum Hall effect.[84][118][119] Later, single graphene layers were also observed directly by electron microscopy.[32] More recently, graphene samples prepared on nickel films, and on both the silicon face and carbon face of silicon carbide, have shown the anomalous quantum Hall effect directly in electrical measurements.[39][40][41][42][42] Graphitic layers on the carbon face of silicon carbide show a clear Dirac spectrum in angle-resolved photoemission experiments, and the anomalous quantum Hall effect is observed in cyclotron resonance and tunneling experiments.[211] Even though graphene on nickel and on silicon carbide have both existed in the laboratory for decades, it was graphene mechanically exfoliated on SiO2 that provided the first proof of the Dirac fermion nature of electrons in graphene.

19

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N.B. This paper reports graphitic flakes that give an additional contrast equivalent of down to ~4A or 3 atomic layers of amorphous carbon. This was the best possible resolution for 1960 TEMs. However, neither then nor today it is possible to argue how many layers were in those flakes. Now we know that the TEM contrast of graphene most

Graphene strongly depends on focusing conditions [Meyer et al, Nature 446, 60 (2007)]. For example, it is impossible to distinguish between suspended monolayer and multilayer graphene by their TEM contrasts, and the only known way is to analyse relative intensities of various diffraction spots. The first reliable TEM observations of monolayers are probably given in refs. 24 and 26 of Geim & Novoselov, Nature Materials 6, 183 (2007).
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External links
Most of graphene papers published by Andre Geim's group are downloadable here (http://onnes.ph.man.ac.uk/ nano/Publications.html#Graphene) Is Graphene the New Silicon? (http://www.nsf.gov/news/news_summ.jsp?cntn_id=111341&org=NSF& from=news) National Science Foundation, March 27, 2008 "Band structure of graphene" (http://www.nanohub.org/resource_files/2005/12/00723/2004.10. 20-l21-ece453.pdf) (PDF). Retrieved 2009-08-15. Graphene portal with daily news and resources (http://www.graphene-info.com/) Antonio H. Castro Neto (12 May 2009). "Pauling's dreams for graphene" (http://physics.aps.org/articles/v2/ 30). N M R Peres and R M Ribeiro (2009). "Focus on Graphene". New Journal of Physics 11 (9): 095002. Bibcode2009NJPh...11i5002P. doi:10.1088/1367-2630/11/9/095002. Online short course: Colloquium on Graphene Physics and Devices (http://nanohub.org/resources/7180) List of Authority Articles on Graphene Theme (http://xstructure.inr.ac.ru/x-bin/auththeme3.py?level=2& index1=181648&skip=0) Short video explanation 'What is Graphene?' (http://vega.org.uk/video/programme/326) Short video 'Graphene and the Carbon Revolution' (http://www.vega.org.uk/video/programme/325) 'Polish team claims leap for wonder material graphene' (http://www.physorg.com/news/ 2011-04-team-material-graphene.html) 'Scientists Find Simple Way to Produce Graphene' (http://www.sciencedaily.com/releases/2011/06/ 110620161308.htm) 'Graphene technology moves closer' (http://www.bbc.co.uk/news/technology-13886438) 'What Graphene offers for future Electronic Devices by Linda Rae' (http://eetimes.com/discussion/other/ 4211323/What-Graphene-Offers-for-Future-Electronic-Devices) 'Nobel Prize Winners Use Keithley' (http://photonics.com/Article.aspx?AID=44755) 'Graphene Shows Promise: Researchers are Looking for New Materials that can take over where Silicon will Leave Off' (http://www.tmworld.com/article/509963-Graphene_shows_promise.php) 'How To Avoid Self-Heating Effects on Nanoscale Devices' (http://www.keithley.com/events/semconfs/ webseminars/nanoseminar3) 'Defects Improve Graphene Conductivity' (http://nanotechweb.org/cws/article/tech/39191) 'Rice University lab shows troop how any carbon source can become valuable graphene' (http://www.media. rice.edu/media/NewsBot.asp?MODE=VIEW&ID=16014&SnID=2124917013)

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Nanocomposite
A nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm), or structures having nano-scale repeat distances between the different phases that make up the material.[1] In the broadest sense this definition can include porous media, colloids, gels and copolymers, but is more usually taken to mean the solid combination of a bulk matrix and nano-dimensional phase(s) differing in properties due to dissimilarities in structure and chemistry. The mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the nanocomposite will differ markedly from that of the component materials. Size limits for these effects have been proposed,[2] <5nm for catalytic activity, <20nm for making a hard magnetic material soft, <50nm for refractive index changes, and <100nm for achieving superparamagnetism, mechanical strengthening or restricting matrix dislocation movement. Nanocomposites are found in nature, for example in the structure of the abalone shell and bone. The use of nanoparticle-rich materials long predates the understanding of the physical and chemical nature of these materials. Jose-Yacaman et al. [3] investigated the origin of the depth of colour and the resistance to acids and bio-corrosion of Maya blue paint, attributing it to a nanoparticle mechanism. From the mid 1950s nanoscale organo-clays have been used to control flow of polymer solutions (e.g. as paint viscosifiers) or the constitution of gels (e.g. as a thickening substance in cosmetics, keeping the preparations in homogeneous form). By the 1970s polymer/clay composites were the topic of textbooks,[4] although the term "nanocomposites" was not in common use. In mechanical terms, nanocomposites differ from conventional composite materials due to the exceptionally high surface to volume ratio of the reinforcing phase and/or its exceptionally high aspect ratio. The reinforcing material can be made up of particles (e.g. minerals), sheets (e.g. exfoliated clay stacks) or fibres (e.g. carbon nanotubes or electrospun fibres). The area of the interface between the matrix and reinforcement phase(s) is typically an order of magnitude greater than for conventional composite materials. The matrix material properties are significantly affected in the vicinity of the reinforcement. Ajayan et al. [1] note that with polymer nanocomposites, properties related to local chemistry, degree of thermoset cure, polymer chain mobility, polymer chain conformation, degree of polymer chain ordering or crystallinity can all vary significantly and continuously from the interface with the reinforcement into the bulk of the matrix. This large amount of reinforcement surface area means that a relatively small amount of nanoscale reinforcement can have an observable effect on the macroscale properties of the composite. For example, adding carbon nanotubes improves the electrical and thermal conductivity. Other kinds of nanoparticulates may result in enhanced optical properties, dielectric properties, heat resistance or mechanical properties such as stiffness, strength and resistance to wear and damage. In general, the nano reinforcement is dispersed into the matrix during processing. The percentage by weight (called mass fraction) of the nanoparticulates introduced can remain very low (on the order of 0.5% to 5%) due to the low filler percolation threshold, especially for the most commonly used non-spherical, high aspect ratio fillers (e.g. nanometer-thin platelets, such as clays, or nanometer-diameter cylinders, such as carbon nanotubes).

Ceramic-matrix nanocomposites
In this group of composites the main part of the volume is occupied by a ceramic, i.e. a chemical compound from the group of oxides, nitrides, borides, silicides etc.. In most cases, ceramic-matrix nanocomposites encompass a metal as the second component. Ideally both components, the metallic one and the ceramic one, are finely dispersed in each other in order to elicit the particular nanoscopic properties. Nanocomposite from these combinations were demonstrated in improving their optical, electrical and magnetic properties [5] as well as tribological, corrosion-resistance and other protective properties.[6] The binary phase diagram of the mixture should be considered in designing ceramic-metal nanocomposites and measures have to be taken to avoid a chemical reaction between both components. The last point mainly is of

Nanocomposite importance for the metallic component that may easily react with the ceramic and thereby loose its metallic character. This is not an easily obeyed constraint, because the preparation of the ceramic component generally requires high process temperatures. The most safe measure thus is to carefully choose immiscible metal and ceramic phases. A good example for such a combination is represented by the ceramic-metal composite of TiO2 and Cu, the mixtures of which were found immiscible over large areas in the Gibbs triangle of Cu-O-Ti.[7] The concept of ceramic-matrix nanocomposites was also applied to thin films that are solid layers of a few nm to some tens of m thickness deposited upon an underlying substrate and that play an important role in the functionalization of technical surfaces. Gas flow sputtering by the hollow cathode technique turned out as a rather effective technique for the preparation of nanocomposite layers. The process operates as a vacuum-based deposition technique and is associated with high deposition rates up to some m/s and the growth of nanoparticles in the gas phase. Nanocomposite layers in the ceramics range of composition were prepared from TiO2 and Cu by the hollow cathode technique [8] that showed a high mechanical hardness, small coefficients of friction and a high resistance to corrosion.

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Metal-matrix nanocomposites
Metal matrix nanocomposites can also define as reinforced metal matrix composites.This kind of composites can be classify as continuous and non continuous reinforced materials.One of the important nanocomposites is Carbon nanotube metal matrix composites which is emerging new materials that are being developed to take advantage of the high tensile strength and electrical conductivity of carbon nanotube materials.Critical to the realization of CNT-MMC possessing optimal properties in these areas are the development of synthetic techniques that are (a) economically producible, (b) provide for a homogeneous dispersion of nanotubes in the metallic matrix, and (c) lead to strong interfacial adhesion between the metallic matrix and the carbon nanotubes.In addition to carbon nanotube metal matrix composites, boron nitride reinforced metal matrix composites and carbon nitride metal matrix composites are the new research areas on metal matrix nanocomposites.[9] Another kind of nanocomposite is the energetic nanocomposite, generally as a hybrid solgel with a silica base, which, when combined with metal oxides and nano-scale aluminium powder, can form superthermite materials.[10][11][12]

Polymer-matrix nanocomposites
In the simplest case, appropriately adding nanoparticulates to a polymer matrix can enhance its performance, often in very dramatic degree, by simply capitalizing on the nature and properties of the nanoscale filler [13] (these materials are better described by the term nanofilled polymer composites [13]). This strategy is particularly effective in yielding high performance composites, when good dispersion of the filler is achieved and the properties of the nanoscale filler are substantially different or better than those of the matrix, for example, reinforcing a polymer matrix by much stiffer nanoparticles [14][15] of ceramics, clays, or carbon nanotubes. It should be noted that the improvement in mechanical properties may not be limited to stiffness or strength. Time-dependent properties could be improved by addition of the nanofillers [16]. Alternatively, the enhanced properties of high performance nanocomposites may be mainly due to the high aspect ratio and/or the high surface area of the fillers,[17][18] since nanoparticulates have extremely high surface area to volume ratios when good dispersion is achieved. Nanoscale dispersion of filler or controlled nanostructures in the composite can introduce new physical properties and novel behaviours that are absent in the unfilled matrices, effectively changing the nature of the original matrix [13] (such composite materials can be better described by the term genuine nanocomposites or hybrids [13]). Some examples of such new properties are fire resistance or flame retardancy [19] and accelerated biodegradability.

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References
[1] P.M. Ajayan, L.S. Schadler, P.V. Braun (2003). Nanocomposite science and technology. Wiley. ISBN3-527-30359-6. [2] Kamigaito, O, What can be improved by nanometer composites? J. Jpn. Soc. Powder Powder Metall. 38:315-21, 1991 in Kelly, A, Concise encyclopedia of composites materials, Elsevier Science Ltd, 1994 [3] Jose-Yacaman, M.; Rendon, L.; Arenas, J.; Serra Puche, M. C. (1996). "Maya Blue Paint: An Ancient Nanostructured Material". Science 273 (5272): 2235. doi:10.1126/science.273.5272.223. PMID8662502. [4] B.K.G. Theng "Formation and Properties of Clay Polymer Complexes", Elsevier, NY 1979; ISBN 978-0-444-41706-0 [5] F. E. Kruis, H. Fissan and A. Peled (1998). "Synthesis of nanoparticles in the gas phase for electronic, optical and magnetic applications a review". J. Aerosol Sci. 29 (56): 511535. doi:10.1016/S0021-8502(97)10032-5. [6] S. Zhang, D. Sun, Y. Fu and H. Du (2003). "Recent advances of superhard nanocomposite coatings: a review". Surf. Coat. Technol. 167 (23): 113119. doi:10.1016/S0257-8972(02)00903-9. [7] G. Effenberg, F. Aldinger and P. Rogl (2001). Ternary Alloys. A Comprehensive Compendium of Evaluated Constitutional Data and Phase Diagrams. Materials Science-International Services. ISBNstatus = May be invalid - please double check. [8] M. Birkholz, U. Albers, and T. Jung (2004). "Nanocomposite layers of ceramic oxides and metals prepared by reactive gas-flow sputtering" (http:/ / www. mariobirkholz. de/ SCT2004. pdf). Surf. Coat. Technol. 179 (23): 279285. doi:10.1016/S0257-8972(03)00865-X. . [9] S. R. Bakshi, D. Lahiri, and A. Argawal, Carbon nanotube reinforced metal matrix composites - A Review, International Materials Reviews, vol. 55, (2010), http:/ / web. eng. fiu. edu/ agarwala/ PDF/ 2010/ 12. pdf [10] Gash, AE. "Making nanostructured pyrotechnics in a Beaker" (http:/ / e-reports-ext. llnl. gov/ pdf/ 247064. pdf) (pdf). . Retrieved 2008-09-28. [11] Gash, AE. "Energetic nanocomposites with sol-gel chemistry: synthesis, safety, and characterization, LLNL UCRL-JC-146739" (http:/ / e-reports-ext. llnl. gov/ pdf/ 244137. pdf) (pdf). . Retrieved 2008-09-28. [12] Ryan, Kevin R.; Gourley, James R.; Jones, Steven E. (2008). "Environmental anomalies at the World Trade Center: evidence for energetic materials". The Environmentalist 29: 56. doi:10.1007/s10669-008-9182-4. [13] Manias, Evangelos (2007). "Nanocomposites: Stiffer by design". Nature Materials 6 (1): 911. doi:10.1038/nmat1812. PMID17199118. [14] Y. Mai, Z. Yu, (2006). Y. Mai, Z. Yu. ed. Polymer Nanocomposites. Woodhead Publ.. ISBN978-1-85573-969-7. [15] "Polymer-Clay Nanocomposites", T. J. Pinnavaia, G. W. Beall (eds.), Wiley, 2001; ISBN 978-0-471-63700-4 [16] Zandiatashbar, Ardavan; Picu, Catalin R.; Koratkar, Nikhil (2012). "Control of Epoxy Creep Using Graphene". Small 8 (11): 1676-1682. doi:10.1002/smll.201102686. [17] Usuki, Arimitsu; Kawasumi, Masaya; Kojima, Yoshitsugu; Okada, Akane; Kurauchi, Toshio; Kamigaito, Osami (1993). "Swelling behavior of montmorillonite cation exchanged for -amino acids by -caprolactam". Journal of Materials Research 8 (5): 1174. doi:10.1557/JMR.1993.1174. [18] Usuki, Arimitsu; Kojima, Yoshitsugu; Kawasumi, Masaya; Okada, Akane; Fukushima, Yoshiaki; Kurauchi, Toshio; Kamigaito, Osami (1993). "Synthesis of nylon 6-clay hybrid". Journal of Materials Research 8 (5): 1179. doi:10.1557/JMR.1993.1179. [19] "Flame Retardant Polymer Nanocomposites" A. B. Morgan, C. A. Wilkie (eds.), Wiley, 2007; ISBN 978-0-471-73426-0

Further reading
Kumar, S. K.; Krishnamoorti, R. (2010). "Nanocomposites: Structure, Phase Behavior, and Properties". Annual Review of Chemical and Biomolecular Engineering 1: 3758. doi:10.1146/annurev-chembioeng-073009-100856. PMID22432572.

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Polymer nanocomposite
Polymer nanoscience is the study and application of nanoscience to polymer-nanoparticle matrices, where nanoparticles are those with at least one dimension of less than 100 nm.

Nanocomposites
Polymer nanocomposites (PNC) consist of a polymer or copolymer having nanoparticles or nanofillers dispersed in the polymer matrix. These may be of different shape (e.g., platelets, fibers, spheroids), but at least one dimension must be in the range of 1 to 50nm. These PNC's belong to the category of multi-phase systems (MPS, viz. blends, composites, and foams) that consume nearly 95% of plastics production. These systems require controlled mixing/compounding, stabilization of the achieved dispersion, orientation of the dispersed phase, and the compounding strategies for all MPS, including PNC, are similar. The transition from micro- to nano-particles lead to change in its physical as well as chemical properties. Two of the major factors in this are the increase in the ratio of the surface area to volume, and the size of the particle. The increase in surface area-to-volume ratio, which increases as the particles get smaller, leads to an increasing dominance of the behavior of atoms on the surface area of particle over that of those interior of the particle. This affects the properties of the particles when they are reacting with other particles. Because of the higher surface area of the nano-particles, the interaction with the other particles within the mixture is more and this increases the strength, heat resistance, etc. and many factors do change for the mixture. An example of a nanopolymer is silicon nanospheres which show quite different characteristics; their size is 40 100nm and they are much harder than silicon, their hardness being between that of sapphire and diamond.

Bio-hybrid polymer nanofibers

Many technical applications of biological objects like proteins, viruses or bacteria such as chromatography, optical information technology, sensorics, catalysis and drug delivery require their immobilization. Carbon nanotubes, gold particles and synthetic polymers are used for this purpose. This immobilization has been achieved predominantly by adsorption or by chemical binding and to a lesser extent by incorporating these objects as guests in host matrices. In the guest host systems, an ideal method for the immobilization of biological objects and their integration into hierarchical architectures should be structured on a nanoscale to facilitate the interactions of biological nano-objects with their environment. Due to the large number of natural or synthetic polymers available and the advanced techniques developed to process such systems to nanofibres, rods, tubes etc. make polymers a good platform for the immobilization of biological objects.[1]

Bio-hybrid nanofibres by electrospinning

Polymer fibers are, in general, produced on a technical scale by extrusion, i.e., a polymer melt or a polymer solution is pumped through cylindrical dies and spun/drawn by a take-up device. The resulting fibers have diameters typically on the 10-m scale or above. To come down in diameter into the range of several hundreds of nanometers or even down to a few nanometers, Electrospinning is today still the leading polymer processing technique available. A strong electric field of the order of 103 V/cm is applied to the polymer solution droplets emerging from a cylindrical die. The electric charges, which are accumulated on the surface of the droplet, cause droplet deformation along the field direction, even though the surface tension counteracts droplet evolution. In supercritical electric fields, the field strength overbears the surface tension and a fluid jet emanates from the droplet tip. The jet is accelerated towards the counter electrode. During this transport phase, the jet is subjected to strong electrically driven circular bending motions that cause a strong elongation and thinning of the jet, a solvent evaporation until, finally, the solid nanofibre is deposited on the counter electrode.

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Bio-hybrid polymer nanotubes by wetting

Electro spinning, co-electrospinning, and the template methods based on nanofibres yield nano-objects which are, in principle, infinitively long. For a broad range of applications including catalysis, tissue engineering, and surface modification of implants this infinite length is an advantage. But in some applications like inhalation therapy or systemic drug delivery, a well-defined length is required. The template method to be described in the following has the advantage such that it allows the preparation of nanotubes and nanorods with very high precision. The method is based on the use of well defined porous templates, such as porous aluminum or silicon. The basic concept of this method is to exploit wetting processes. A polymer melt or solution is brought into contact with the pores located in materials characterized by high energy surfaces such as aluminum or silicon. Wetting sets in and covers the walls of the pores with a thin film with a thickness of the order of a few tens of nanometers. Gravity does not play a role, as it is obvious from the fact that wetting takes place independent of the orientation of the pores relative to the direction of gravity. The exact process is still not understood theoretically in detail but its known from experiments that low molar mass systems tend to fill the pores completely, whereas polymers of sufficient chain length just cover the walls. This process happens typically within a minute for temperatures about 50 K above the melting temperature or glass transition temperature, even for highly viscous polymers, such as, for instance, polytetrafluoroethylene, and this holds even for pores with an aspect ratio as large as 10,000. The complete filling, on the other hand, takes days. To obtain nanotubes, the polymer/template system is cooled down to room temperature or the solvent is evaporated, yielding pores covered with solid layers. The resulting tubes can be removed by mechanical forces for tubes up to 10m in length, i.e., by just drawing them out from the pores or by selectively dissolving the template. The diameter of the nanotubes, the distribution of the diameter, the homogeneity along the tubes, and the lengths can be controlled.

Applications
The nanofibres, hollow nanofibres, core-shell nanofibres, and nanorods or nanotubes produced have a great potential for a broad range of applications including homogeneous and heterogeneous catalysis, sensorics, filter applications, and optoelectronics. Here we will just consider a limited set of applications related to life science. Tissue engineering This is mainly concerned with the replacement of tissues which have been destroyed by sickness or accidents or other artificial means. The examples are skin, bone, cartilage, blood vessels and may be even organs. This technique involves providing a scaffold on which cells are added and the scaffold should provide favorable conditions for the growth of the same. Nanofibres have been found to provide very good conditions for the growth of such cells, one of the reasons being that fibrillar structures can be found on many tissues which allow the cells to attach strongly to the fibers and grow along them as shown. Delivery from compartmented nanotubes Nano tubes are also used for carrying drugs in general therapy and in tumor therapy in particular. The role of them is to protect the drugs from destruction in blood stream, to control the delivery with a well-defined release kinetics, and in ideal cases, to provide vector-targeting properties or release mechanism by external or internal stimuli. Rod or tube-like, rather than nearly spherical, nanocarriers may offer additional advantages in terms of drug delivery systems. Such drug carrier particles possess additional choice of the axial ratio, the curvature, and the all-sweeping hydrodynamic-related rotation, and they can be modified chemically at the inner surface, the outer surface, and at the end planes in a very selective way. Nanotubes prepared with a responsive polymer attached to the tube opening allow the control of access to and release from the tube. Furthermore, nanotubes can also be prepared showing a gradient in its chemical composition along the length of the tube. Compartmented drug release systems were prepared based on nanotubes or nanofibres. Nanotubes and nanofibres, for instance, which contained fluorescent albumin with dog-fluorescein isothiocyanate were prepared as a model

Polymer nanocomposite drug, as well as super paramagnetic nanoparticles composed of iron oxide or nickel ferrite. The presence of the magnetic nanoparticles allowed, first of all, the guiding of the nanotubes to specific locations in the body by external magnetic fields. Super paramagnetic particles are known to display strong interactions with external magnetic fields leading to large saturation magnetizations. In addition, by using periodically varying magnetic fields, the nanoparticles were heated up to provide, thus, a trigger for drug release. The presence of the model drug was established by fluorescence spectroscopy and the same holds for the analysis of the model drug released from the nanotubes. Immobilization of proteins Core shell fibers of nano particles with fluid cores and solid shells can be used to entrap biological objects such as proteins, viruses or bacteria in conditions which do not affect their functions. This effect can be used among others for biosensor applications. For example Green Fluorescent Protein is immobilized in nanostructured fibres providing large surface areas and short distances for the analyte to approach the sensor protein. With respect to using such fibers for sensor applications fluorescence of the core shell fibers was found to decay rapidly as the fibers were immersed into a solution containing urea: urea permeates through the wall into the core where it causes denaturation of the GFP. This simple experiment reveals that core-shell fibers are promising objects for preparing biosensors based on biological objects. Polymer nanostructured fibers, core-shell fibers, hollow fibers, and nanorods and nanotubes provide a platform for a broad range of applications both in material science as well as in life science. Biological objects of different complexity and synthetic objects carrying specific functions can be incorporated into such nanostructured polymer systems while keeping their specific functions vital. Biosensors, tissue engineering, drug delivery, or enzymatic catalysis is just a few of the possible examples. The incorporation of viruses and bacteria all the way up to microorganism should not really pose a problem and the applications coming from such biohybrid systems should be tremendous.[2]

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Size and pressure effects on nanopolymers

The size- and pressure- dependent glass transition temperatures of free-standing films or supported films having weak interactions with substrates decreases with decreasing of pressure and size. However, the glass transition temperature of supported films having strong interaction with substrates increases of pressure and the decrease of size. Different models like two layer model, three layer model, Tg (D, 0) 1/D and some more models relating specific heat, density and thermal expansion are used to obtain the experimental results on nanopolymers and even some observations like freezing of films due to memory effects in the visco-elastic eigenmodels of the films, and finite effects of the small molecule glass are observed. To describe Tg (D, 0) function of polymers more generally, a simple and unified model recently is provided based on the size-dependent melting temperature of crystals and Lindemann's criterion where g is the root of mean squared displacement of surface and interior molecules of glasses at Tg (D, 0), = s2 (D, 0) / v2 (D, 0) with subscripts s and v denoting surface and volume, respectively. For a nanoparticle, D has a usual meaning of diameter, for a nanowire, D is taken as its diameter, and for a thin film, D denotes its thickness. D0 denotes a critical diameter at which all molecules of a low dimensional glass are located on its surface.[3]

Tg (D, 0) / Tg (, 0) g2 (, 0) / g2 (D, 0)

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Conclusion
The devices that utilize the properties of low dimensional objects such as nanoparticles are promising due to the possibility of tailoring a number of electrophysical, optical and magnetic properties changing the size of nanoparticles, which can be controlled during the synthesis. In the case of polymer nanocomposites we can utilize the properties of disordered systems. Here recent developments in the field of polymer nano-composites and some of their applications have been reviewed. Though there is much utilization in this field, there are many limitations also. For example in the release of drugs using nanofibres, cannot be controlled independently and a burst release is usually the case, whereas a more linear release is required. Let us now consider future aspects in this field. There is a possibility of building ordered arrays of nanoparticles in the polymer matrix. A number of possibilities also exist to manufacture the nanocomposite circuit boards. An even more attractive method exists to utilize polymer nanocomposites for neural networks applications. Another promising area of development is optoelectronics and optical computing. The single domain nature and super paramagnetic behavior of nanoparticles containing ferromagnetic metals could be possibly utilized for magneto-optical storage media manufacturing.

References
[1] A. Greiner, J. H. Wendorff , A. L. Yarin and E. Zussman, (2006), Biohybrid nanosystems with polymer nanofibers and nanotubes, Applied microbial biotechnology 71:387-393 [2] D.Y.Godovsky(2000) Applications of Polymer-Nanocomposites. Advances in Polymer science vol. 153:165-205 [3] Lang, X. Y.; Zhang, G. H.; Lian, J. S.; Jiang, Q. (2006). "Size and pressure effects on glass transition temperature of poly (methyl methacrylate) thin films". Thin Solid Films 497 (1-2): 333. Bibcode2006TSF...497..333L. doi:10.1016/j.tsf.2005.10.001.

Polymerization
In polymer chemistry, polymerization is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks.[1][2][3] There are many forms of polymerization and different systems exist to categorize them.
An example of alkene polymerization, in which each Styrene monomer unit's double bond reforms as a single bond with another styrene monomer and forms polystyrene.

Introduction
Homopolymers Copolymers
In chemical compounds, polymerization occurs via a variety of reaction mechanisms that vary in complexity due to functional groups present in reacting compounds[4] and their inherent steric effects. In more straightforward polymerization, alkenes, which are relatively stable due to bonding between carbon atoms, form polymers through relatively simple radical reactions; in contrast, more complex reactions such as those that involve

Polymerization substitution at the carbonyl group require more complex synthesis due to the way in which reacting molecules polymerize.[4] As alkenes can be formed in somewhat straightforward reaction mechanisms, they form useful compounds such as polyethylene and polyvinyl chloride (PVC) when undergoing radical reactions,[4] which are produced in high tonnages each year[4] due to their usefulness in manufacturing processes of commercial products, such as piping, insulation and packaging. In general, polymers such as PVC are referred to as "homopolymers," as they consist of repeated long chains or structures of the same monomer unit, whereas polymers that consist of more than one molecule are referred to as copolymers (or co-polymers).[5] Other monomer units, such as formaldehyde hydrates or simple aldehydes, are able to polymerize themselves at quite low temperatures (>80C) to form trimers;[4] molecules consisting of 3 monomer units, which can cyclize to form ring cyclic structures, or undergo further reactions to form tetramers,[4] or 4 monomer-unit compounds. Further compounds either being referred to as oligomers[4] in smaller molecules. Generally, because formaldehyde is an exceptionally reactive electrophile it allows nucleophillic addition of hemiacetal intermediates, which are in general short-lived and relatively unstable "mid-stage" compounds that react with other molecules present to form more stable polymeric compounds. Polymerization that is not sufficiently moderated and proceeds at a fast rate can be very hazardous. This phenomenon is known as hazardous polymerization and can cause fires and explosions.

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Step-growth
Step-growth polymers are defined as polymers formed by the stepwise reaction between functional groups of monomers, usually containing heteroatoms such as nitrogen or oxygen. Most step-growth polymers are also classified as condensation polymers, but not all step-growth polymers (like polyurethanes formed from isocyanate and alcohol bifunctional monomers) release condensates; in this case, we talk about addition polymers. Step-growth polymers increase in molecular weight at a very slow rate at lower conversions and reach moderately high molecular weights only at very high conversion (i.e., >95%). To alleviate inconsistencies in these naming methods, adjusted definitions for condensation and addition polymers have been developed. A condensation polymer is defined as a polymer that involves loss of small molecules during its synthesis, or contains heteroatoms as part of its backbone chain, or its repeat unit does not contain all the atoms present in the hypothetical monomer to which it can be degraded.

Chain-growth
Chain-growth polymerization (or addition polymerization) involves the linking together of molecules incorporating double or triple carbon-carbon bonds. These unsaturated monomers (the identical molecules that make up the polymers) have extra internal bonds that are able to break and link up with other monomers to form a repeating chain, whose backbone typically contains only carbon atoms. Chain-growth polymerization is involved in the manufacture of polymers such as polyethylene, polypropylene, and polyvinyl chloride (PVC). A special case of chain-growth polymerization leads to living polymerization. In the radical polymerization of ethylene, its bond is broken, and the two electrons rearrange to create a new propagating center like the one that attacked it. The form this propagating center takes depends on the specific type of addition mechanism. There are several mechanisms through which this can be initiated. The free radical mechanism is one of the first methods to be used. Free radicals are very reactive atoms or molecules that have unpaired electrons. Taking the polymerization of ethylene as an example, the free radical mechanism can be divided in to three stages: chain initiation, chain propagation, and chain termination.

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Free radical addition polymerization of ethylene must take place at high temperatures and pressures, approximately 300C and 2000 atm. While most other free radical polymerizations do not require such Polymerization of ethylene extreme temperatures and pressures, they do tend to lack control. One effect of this lack of control is a high degree of branching. Also, as termination occurs randomly, when two chains collide, it is impossible to control the length of individual chains. A newer method of polymerization similar to free radical, but allowing more control involves the Ziegler-Natta catalyst, especially with respect to polymer branching. Other forms of chain growth polymerization include cationic addition polymerization and anionic addition polymerization. While not used to a large extent in industry yet due to stringent reaction conditions such as lack of water and oxygen, these methods provide ways to polymerize some monomers that cannot be polymerized by free radical methods such as polypropylene. Cationic and anionic mechanisms are also more ideally suited for living polymerizations, although free radical living polymerizations have also been developed. Esters of acrylic acid contain a carbon-carbon double bond which is conjugated to an ester group. This allows the possibility of both types of polymerization mechanism. An acrylic ester by itself can undergo chain-growth polymerization to form a homopolymer with a carbon-carbon backbone, such as poly(methyl methacrylate). Also, however, certain acrylic esters can react with diamine monomers by nucleophilic conjugate addition of amine groups to acrylic C=C bonds. In this case the polymerization proceeds by step-growth and the products are poly(beta-amino ester) copolymers, with backbones containing nitrogen (as amine) and oxygen (as ester) as well as carbon.[6]

References
[1] Introduction to Polymers 1987 R.J. Young Chapman & Hall ISBN 0-412-22170-5 [2] International Union of Pure and Applied Chemistry, et al. (2000) IUPAC Gold Book, Polymerization (http:/ / goldbook. iupac. org/ P04740. html) [3] Clayden, J., Greeves, N. et al. (2000). "Organic chemistry" Oxford [4] Clayden, J., Greeves, N. et al. (2000), p1450-1466 [5] J.M.G. Cowie "Polymers: Chemistry and Physics of Modern Materials (Chapman and Hall, 2d ed. 1991) p.4 [6] D.M. Lynn and R. Langer (2000), J. Am. Chem. Soc. vol.122, p.10761 (http:/ / pubs. acs. org/ doi/ abs/ 10. 1021/ ja0015388) Degradable Poly(-amino esters): Synthesis, Characterization, and Self-Assembly with Plasmid DNA

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