Breakdown of the adiabatic Born-Oppenheimer approximation in graphene.
TL;DR: It is shown that ABO fails in graphene, a zero-bandgap semiconductor that becomes a metal if the Fermi energy is tuned applying a gate voltage, Vg, which induces a stiffening of the Raman G peak that cannot be described within ABO.
Abstract: The adiabatic Born-Oppenheimer approximation (ABO) has been the standard ansatz to describe the interaction between electrons and nuclei since the early days of quantum mechanics. ABO assumes that the lighter electrons adjust adiabatically to the motion of the heavier nuclei, remaining at any time in their instantaneous ground state. ABO is well justified when the energy gap between ground and excited electronic states is larger than the energy scale of the nuclear motion. In metals, the gap is zero and phenomena beyond ABO (such as phonon-mediated superconductivity or phonon-induced renormalization of the electronic properties) occur. The use of ABO to describe lattice motion in metals is, therefore, questionable. In spite of this, ABO has proved effective for the accurate determination of chemical reactions, molecular dynamics and phonon frequencies in a wide range of metallic systems. Here, we show that ABO fails in graphene. Graphene, recently discovered in the free state, is a zero-bandgap semiconductor that becomes a metal if the Fermi energy is tuned applying a gate voltage, Vg. This induces a stiffening of the Raman G peak that cannot be described within ABO.
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TL;DR: In this paper, the basic theoretical aspects of graphene, a one-atom-thick allotrope of carbon, with unusual two-dimensional Dirac-like electronic excitations, are discussed.
Abstract: This article reviews the basic theoretical aspects of graphene, a one-atom-thick allotrope of carbon, with unusual two-dimensional Dirac-like electronic excitations. The Dirac electrons can be controlled by application of external electric and magnetic fields, or by altering sample geometry and/or topology. The Dirac electrons behave in unusual ways in tunneling, confinement, and the integer quantum Hall effect. The electronic properties of graphene stacks are discussed and vary with stacking order and number of layers. Edge (surface) states in graphene depend on the edge termination (zigzag or armchair) and affect the physical properties of nanoribbons. Different types of disorder modify the Dirac equation leading to unusual spectroscopic and transport properties. The effects of electron-electron and electron-phonon interactions in single layer and multilayer graphene are also presented.
20,824 citations
Cites background or methods from "Breakdown of the adiabatic Born-Opp..."
...…a very important role be ause it allows the iden-ti ation of the number of planes (Ferrari et al., 2006;Graf et al., 2007; Gupta et al., 2006; Pisana et al., 2007;Yan et al., 2007), and the study of the opti al phononmodes in graphene, parti ularly the ones in the enter ofthe BZ with…...
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...Thisamazing result has been observed experimentally by Ra-man spe tros opy (Pisana et al., 2007; Yan et al., 2007)....
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TL;DR: The extremely high value of the thermal conductivity suggests that graphene can outperform carbon nanotubes in heat conduction and establishes graphene as an excellent material for thermal management.
Abstract: We report the measurement of the thermal conductivity of a suspended single-layer graphene. The room temperature values of the thermal conductivity in the range ∼(4.84 ± 0.44) × 103 to (5.30 ± 0.48) × 103 W/mK were extracted for a single-layer graphene from the dependence of the Raman G peak frequency on the excitation laser power and independently measured G peak temperature coefficient. The extremely high value of the thermal conductivity suggests that graphene can outperform carbon nanotubes in heat conduction. The superb thermal conduction property of graphene is beneficial for the proposed electronic applications and establishes graphene as an excellent material for thermal management.
11,878 citations
TL;DR: An overview of the synthesis, properties, and applications of graphene and related materials (primarily, graphite oxide and its colloidal suspensions and materials made from them), from a materials science perspective.
Abstract: There is intense interest in graphene in fields such as physics, chemistry, and materials science, among others. Interest in graphene's exceptional physical properties, chemical tunability, and potential for applications has generated thousands of publications and an accelerating pace of research, making review of such research timely. Here is an overview of the synthesis, properties, and applications of graphene and related materials (primarily, graphite oxide and its colloidal suspensions and materials made from them), from a materials science perspective.
8,919 citations
TL;DR: In this article, the authors focus on the origin of the D and G peaks and the second order of D peak and show that the G and 2 D Raman peaks change in shape, position and relative intensity with number of graphene layers.
6,496 citations
TL;DR: The state of the art, future directions and open questions in Raman spectroscopy of graphene are reviewed, and essential physical processes whose importance has only recently been recognized are described.
Abstract: Raman spectroscopy is an integral part of graphene research. It is used to determine the number and orientation of layers, the quality and types of edge, and the effects of perturbations, such as electric and magnetic fields, strain, doping, disorder and functional groups. This, in turn, provides insight into all sp(2)-bonded carbon allotropes, because graphene is their fundamental building block. Here we review the state of the art, future directions and open questions in Raman spectroscopy of graphene. We describe essential physical processes whose importance has only recently been recognized, such as the various types of resonance at play, and the role of quantum interference. We update all basic concepts and notations, and propose a terminology that is able to describe any result in literature. We finally highlight the potential of Raman spectroscopy for layered materials other than graphene.
5,673 citations
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TL;DR: Monocrystalline graphitic films are found to be a two-dimensional semimetal with a tiny overlap between valence and conductance bands and they exhibit a strong ambipolar electric field effect.
Abstract: We describe monocrystalline graphitic films, which are a few atoms thick but are nonetheless stable under ambient conditions, metallic, and of remarkably high quality. The films are found to be a two-dimensional semimetal with a tiny overlap between valence and conductance bands, and they exhibit a strong ambipolar electric field effect such that electrons and holes in concentrations up to 10 13 per square centimeter and with room-temperature mobilities of ∼10,000 square centimeters per volt-second can be induced by applying gate voltage.
55,532 citations
"Breakdown of the adiabatic Born-Opp..." refers background in this paper
...Graphene, recently discovered in the free state [11, 12], is a zero band-gap semiconductor [13], which becomes a metal if the Fermi energy is tuned applying a gate-voltage Vg [14, 12 ]....
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...with the geometry of the resulting capacitor [ 12 , 11, 14]....
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...The resulting devices are characterized by electric-field-effect measurements [ 12 , 14, 22], yielding a charge carrier mobility � of 5,000 to 10,000 cm2/Vs at 295K and a zero-bias (Vg=0) doping of ∼1012 cm−2 [23]....
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...Graphene, recently discovered in the free state [11, 12 ], is a zero band-gap semiconductor [13], which becomes a metal if the Fermi energy is tuned applying a gate-voltage Vg [14, 12]....
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TL;DR: This study reports an experimental study of a condensed-matter system (graphene, a single atomic layer of carbon) in which electron transport is essentially governed by Dirac's (relativistic) equation and reveals a variety of unusual phenomena that are characteristic of two-dimensional Dirac fermions.
Abstract: Quantum electrodynamics (resulting from the merger of quantum mechanics and relativity theory) has provided a clear understanding of phenomena ranging from particle physics to cosmology and from astrophysics to quantum chemistry. The ideas underlying quantum electrodynamics also influence the theory of condensed matter, but quantum relativistic effects are usually minute in the known experimental systems that can be described accurately by the non-relativistic Schrodinger equation. Here we report an experimental study of a condensed-matter system (graphene, a single atomic layer of carbon) in which electron transport is essentially governed by Dirac's (relativistic) equation. The charge carriers in graphene mimic relativistic particles with zero rest mass and have an effective 'speed of light' c* approximately 10(6) m s(-1). Our study reveals a variety of unusual phenomena that are characteristic of two-dimensional Dirac fermions. In particular we have observed the following: first, graphene's conductivity never falls below a minimum value corresponding to the quantum unit of conductance, even when concentrations of charge carriers tend to zero; second, the integer quantum Hall effect in graphene is anomalous in that it occurs at half-integer filling factors; and third, the cyclotron mass m(c) of massless carriers in graphene is described by E = m(c)c*2. This two-dimensional system is not only interesting in itself but also allows access to the subtle and rich physics of quantum electrodynamics in a bench-top experiment.
18,958 citations
"Breakdown of the adiabatic Born-Opp..." refers background in this paper
...with the geometry of the resulting capacitor [12, 11, 14 ]....
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...The resulting devices are characterized by electric-field-effect measurements [12, 14 , 22], yielding a charge carrier mobility � of 5,000 to 10,000 cm2/Vs at 295K and a zero-bias (Vg=0) doping of ∼1012 cm−2 [23]....
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...Graphene, recently discovered in the free state [11, 12], is a zero band-gap semiconductor [13], which becomes a metal if the Fermi energy is tuned applying a gate-voltage Vg [ 14 , 12]....
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TL;DR: This work shows that graphene's electronic structure is captured in its Raman spectrum that clearly evolves with the number of layers, and allows unambiguous, high-throughput, nondestructive identification of graphene layers, which is critically lacking in this emerging research area.
Abstract: Graphene is the two-dimensional building block for carbon allotropes of every other dimensionality We show that its electronic structure is captured in its Raman spectrum that clearly evolves with the number of layers The D peak second order changes in shape, width, and position for an increasing number of layers, reflecting the change in the electron bands via a double resonant Raman process The G peak slightly down-shifts This allows unambiguous, high-throughput, nondestructive identification of graphene layers, which is critically lacking in this emerging research area
13,474 citations
TL;DR: In this paper, an experimental investigation of magneto-transport in a high-mobility single layer of Graphene is presented, where an unusual half-integer quantum Hall effect for both electron and hole carriers in graphene is observed.
Abstract: When electrons are confined in two-dimensional materials, quantum-mechanically enhanced transport phenomena such as the quantum Hall effect can be observed. Graphene, consisting of an isolated single atomic layer of graphite, is an ideal realization of such a two-dimensional system. However, its behaviour is expected to differ markedly from the well-studied case of quantum wells in conventional semiconductor interfaces. This difference arises from the unique electronic properties of graphene, which exhibits electron–hole degeneracy and vanishing carrier mass near the point of charge neutrality1,2. Indeed, a distinctive half-integer quantum Hall effect has been predicted3,4,5 theoretically, as has the existence of a non-zero Berry's phase (a geometric quantum phase) of the electron wavefunction—a consequence of the exceptional topology of the graphene band structure6,7. Recent advances in micromechanical extraction and fabrication techniques for graphite structures8,9,10,11,12 now permit such exotic two-dimensional electron systems to be probed experimentally. Here we report an experimental investigation of magneto-transport in a high-mobility single layer of graphene. Adjusting the chemical potential with the use of the electric field effect, we observe an unusual half-integer quantum Hall effect for both electron and hole carriers in graphene. The relevance of Berry's phase to these experiments is confirmed by magneto-oscillations. In addition to their purely scientific interest, these unusual quantum transport phenomena may lead to new applications in carbon-based electronic and magneto-electronic devices.
11,122 citations
TL;DR: By using micromechanical cleavage, a variety of 2D crystals including single layers of boron nitride, graphite, several dichalcogenides, and complex oxides are prepared and studied.
Abstract: We report free-standing atomic crystals that are strictly 2D and can be viewed as individual atomic planes pulled out of bulk crystals or as unrolled single-wall nanotubes. By using micromechanical cleavage, we have prepared and studied a variety of 2D crystals including single layers of boron nitride, graphite, several dichalcogenides, and complex oxides. These atomically thin sheets (essentially gigantic 2D molecules unprotected from the immediate environment) are stable under ambient conditions, exhibit high crystal quality, and are continuous on a macroscopic scale.
10,586 citations
"Breakdown of the adiabatic Born-Opp..." refers background in this paper
...Graphene, recently discovered in the free state [ 11 , 12], is a zero band-gap semiconductor [13], which becomes a metal if the Fermi energy is tuned applying a gate-voltage Vg [14, 12]....
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...[ 11 ]. This allows us to obtain graphene monocrystals exceeding 30 microns in size....
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...with the geometry of the resulting capacitor [12, 11 , 14]....
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