The topology of electronic and phonon band structures of graphene is well studied and known to exhibit a Dirac cone at the K point of the Brillouin zone. Here, we applied inelastic x-ray scattering (IXS) along with $\textit{ab initio}$ calculations to investigate phonon topology in graphite, the 3D analogue of graphene. We identified a pair of modes that form a very weakly gapped linear anticrossing at the K point that can be essentially viewed as a Dirac cone approximant. The IXS intensity in the vicinity of the quasi-Dirac point reveals a harmonic modulation of the phonon spectral weight above and below the Dirac energy, which was previously proposed as an experimental fingerprint of the nontrivial topology. We illustrate how the topological winding of IXS intensity can be understood in terms of atomic displacements, and highlight that the intensity winding is not in fact sensitive in telling quasi- and true Dirac points apart.
Thermal Hall conductivity of semimetallic graphite dominated by ambipolar phonon drag
Wuhan National High Magnetic Field Center, School of Physics, Huazhong University of Science and Technology（华中科技大学物理学院）；Laboratoire de Physique et d’Étude des Matériaux (ESPCI - CNRS - Sorbonne Université), PSL Research University（巴黎高等物理化工学院-法国国家科学研究中心-索邦大学物质物理与研究实验室）
Allotropes of carbon, such as diamond and graphene, are among the best conductors of heat. We monitored the evolution of thermal conductivity in thin graphite as a function of temperature and thickness and found an intimate link between high conductivity, thickness, and phonon hydrodynamics. The room temperature in-plane thermal conductivity of 8.5-micrometer-thick graphite was 4300 watts per meter-kelvin-a value well above that for diamond and slightly larger than in isotopically purified graphene. Warming enhances thermal diffusivity across a wide temperature range, supporting partially hydr…
Time-resolved Raman spectroscopy has been applied to probe the anharmonic coupling and electron-phonon interaction of optical phonons in graphite. From the decay of the transient anti-Stokes scattering of the G-mode following ultrafast excitation, we measured a lifetime of 2.2+/-0.1ps for zone-center optical phonons. We also observed a transient stiffening of G-mode phonons, an effect attributed to the reduction of the electron-phonon coupling for high electronic temperatures.
Using first-principles modeling, we investigate how phonon transport evolves in layered/van der Waals materials when going from 3D to 2D, or vice versa, by gradually pulling apart the atomic layers in graphite to form graphene. Focus is placed on identifying the features impacting thermal conductivity that are likely shared with other layered materials. The thermal conductivity $κ$ of graphite is found to be lower than that of graphene mainly due to changes in the phonon dispersion driven by van der Waals coupling. Specifically, as the atomic layers are brought closer together, the acoustic fl…
Magneto-Raman scattering experiments from the surface of graphite reveal novel features associated to purely electronic excitations which are observed in addition to phonon-mediated resonances. Graphene-like and graphite domains are identified through experiments with $\sim 1μm$ spatial resolution performed in magnetic fields up to 32T. Polarization resolved measurements emphasize the characteristic selection rules for electronic transitions in graphene. Graphene on graphite displays the unexpected hybridization between optical phonon and symmetric across the Dirac point inter Landau level tra…
A simple model for flexural phonons in graphite (and graphene, corresponding to the limiting case of infinite distance between carbon planes) is proposed, in which the local dipolar moment is assumed to be proportional to the curvature of the carbon sheets. Explicit expressions for dispersion curves with full account for the long-range dipolar interaction forces are given and fitted to the experimental data using a single adjustable parameter of the theory. This parameter is expected to depend on the ground state configuration of molecular $π$-orbitals, the same both for graphite and for graph…
Coherent coupling of Dirac fermion magneto-excitons with an optical phonon is observed in graphite as marked magnetic-field dependent splittings and anti-crossing behavior of the two coupled modes. The sharp magneto-phonon resonance occurs in regions of the graphite sample with properties of superior single-layer graphene having enhanced lifetimes of Dirac fermions. The greatly reduced carrier broadening to values below the graphene electron-phonon coupling constant explains the appearance of sharp resonances that reveal a fundamental interaction of Dirac fermions.
Indirect transitions of electrons in graphene and graphite are investigated by means of angle-resolved photoemission spectroscopy (ARPES) with several different incident photon energies and light polarizations. The theoretical calculations of the indirect transition for graphene and graphite are compared with the experimental measurements for highly-oriented pyrolytic graphite and a single-crystal of graphite. The dispersion relations for the transverse optical (TO) and the out-of-plane longitudinal acoustic (ZA) phonon modes of graphite and the TO phonon mode of graphene can be extracted from…
In the hydrodynamic regime, phonons drift with a nonzero collective velocity under a temperature gradient, reminiscent of viscous gas and fluid flow. The study of hydrodynamic phonon transport has spanned over half a century but has been mostly limited to cryogenic temperatures (~1 K) and more recently to low-dimensional materials. Here, we identify graphite as a three-dimensional material that supports phonon hydrodynamics at significantly higher temperatures (~100 K) based on first-principles calculations. In particular, by solving the Boltzmann equation for phonon transport in graphite ribb…
Heat conduction in graphite has been studied for decades because of its exceptionally large thermal anisotropy. While the bulk thermal conductivities along the in-plane and cross-plane directions are well known, less understood are the microscopic properties of the thermal phonons responsible for heat conduction. In particular, recent experimental and computational works indicate that the average phonon mean free path (MFP) along the c-axis is considerably larger than that estimated by kinetic theory, but the distribution of MFPs remains unknown. Here, we report the first quantitative measurem…
Stacking graphene sheets forms graphite. Two in-plane vibrational modes of graphite, E1u and E2g(2), are derived from graphene E2g mode, the shifts of which under compression are all considered as results of in-plane bond shortening. Values of Gruneisen parameter have been reported to quantify such relation. However, the reason why the shift rates of these three modes with pressure differ is unclear. In this work, we introduce a new parameter to quantify the contribution of out-of-plane strain to the in-plane vibrational frequencies, suggesting that the compression of π-electrons plays a non-…
The differential conductance in a suspended few layered graphene sample is fou nd to exhibit a series of quasi-periodic sharp dips as a function of bias at l ow temperature. We show that they can be understood within a simple model of dyn amical Coulomb blockade where energy exchanges take place between the charge carriers transmitted trough the sample and a dissipative electromagnetic envir onment with a resonant phonon mode strongly coupled to the electrons.
We perform Raman scattering experiments on natural graphite in magnetic fields up to 45 T, observing a series of peaks due to interband electronic excitations over a much broader magnetic field range than previously reported. We also explore electron-phonon coupling in graphite via magnetophonon resonances. The Raman G peak shifts and splits as a function of magnetic field, due to the magnetically tuned coupling of the E2g optical phonons with the K- and H-point inter-Landau-level excitations. The analysis of the observed anticrossing behavior allows us to determine the electron-phonon couplin…
Boundary scattering of thermal phonons in thin solid films is typically analyzed using Fuchs-Sondheimer theory, which provides a simple equation to calculate the reduction of thermal conductivity as a function of the film thickness. However, this widely-used equation is not applicable to highly anisotropic solids like graphite because it assumes the phonon dispersion is isotropic. Here, we derive a generalization of the Fuchs-Sondheimer equation for solids with arbitrary dispersion relations and examine its predictions for graphite. We find that the isotropic equation vastly overestimates the …
We compute electron-phonon coupling (EPC) of selected phonon modes in graphene and graphite using various ab-initio methods. The inclusion of non-local exchange-correlation effects within the GW approach strongly renormalizes the square EPC of the A$'_1$ {\bf K} mode by almost 80$%$ with respect to density functional theory in the LDA and GGA approximations. Within GW, the phonon slope of the A$'_1$ {\bf K} mode is almost two times larger than in GGA and LDA, in agreement with phonon dispersions from inelastic x-ray scattering and Raman spectroscopy. The hybrid B3LYP functional overestimates t…
The magneto-phonon resonance or MPR occurs in semiconductor materials when the energy spacing between Landau levels is continuously tuned to cross the energy of an optical phonon mode. MPRs have been largely explored in bulk semiconductors, in two-dimensional systems and in quantum dots. Recently there has been significant interest in the MPR interactions of the Dirac fermion magnetoexcitons in graphene, and a rich splitting and anti-crossing phenomena of the even parity E2g long wavelength optical phonon mode have been theoretically proposed and experimentally observed. The MPR has been found…
We use polarized magneto-Raman scattering to study purely electronic excitations and the electron-phonon coupling in bulk graphite. At a temperature of 4.2 K and in magnetic fields up to 28 T we observe $K$-point electronic excitations involving Landau bands with $Δ|n|=0$ and with $Δ|n|=\pm2$ that can be selected by controlling the angular momentum of the excitation laser and of the scattered light. The magneto-phonon effect involving the $E_{2g}$ optical phonon and $K$-point inter Landau bands electronic excitations with $Δ|n|=\pm1$ is revealed and analyzed within a model taking into account …
Time dynamics of photoexcited electron-hole pairs is important for a number of technologies, in particular solar cells. We combined ultrafast pump-probe Raman scattering and photoemission to directly follow electron-hole excitations as well as the G-phonon in graphite after an excitation by an intense laser pulse. This phonon is known to couple relatively strongly to electrons. Cross-correlating effective electronic and phonon temperatures places new constraints on model-based fits. The accepted two-temperature model predicts that G-phonon population should start to increase as soon as excited…
The authors proposed a simple model for the lattice thermal conductivity of graphene in the framework of Klemens approximation. The Gruneisen parameters were introduced separately for the longitudinal and transverse phonon branches through averaging over phonon modes obtained from the first-principles. The calculations show that Umklapp-limited thermal conductivity of graphene grows with the increasing linear dimensions of graphene flakes and can exceed that of the basal planes of bulk graphite when the flake size is on the order of few micrometers. The obtained results are in agreement with e…
We study the thermal transport properties of twisted-layer graphite nanofibers. We show that in the presence of a twisted layer, the phonon thermal conductance of a graphite nanofiber varies remarkably with the twisted angle and can reach minimum values either at two critical angles $θ_1$ and $θ_2$ that conform to the rule $θ_1$ + $θ_1$ = $180^0$ or exactly at the angle $θ$ = $90^0$. A reduction of roughly 50% of the phonon thermal conductance can be achieved in some structures. We unveil that the twisting effect mainly influences the optical modes, leaving almost unaltered the acoustic ones. …
The thermal properties of anisotropic crystals are of both fundamental and practical interest, but transport phenomena in anisotropic materials such as graphite remain poorly understood because solutions of the Boltzmann equation often assume isotropy. Here, we extend an analytical solution of the Boltzmann equation to highly anisotropic solids and examine its predictions for graphite. We show that the phonon mean free paths in the cross-plane direction can be comparable to those in the in-plane direction despite the low cross-plane thermal conductivity, which instead arises primarily from the…
We report low temperature high magnetic field scanning tunneling microscopy and spectroscopy of graphene flakes on graphite that exhibit the structural and electronic properties of graphene decoupled from the substrate. Pronounced peaks in the tunneling spectra develop with field revealing a Landau level sequence that provides a direct way to identify graphene and to determine the degree of its coupling to the substrate. The Fermi velocity and quasiparticle lifetime, obtained from the positions and width of the peaks, provide access to the electron-phonon and electron-electron interactions.
Results of room temperature Raman scattering studies of ultrathin graphitic films supported on Si (111)/SiO2 substrates are reported. The results are significantly different from those known for graphite. Spectra were collected using 514 nm radiation on films containing from n=1 to 20 graphene layers, as determined by atomic force microscopy. Both the 1st and 2nd order Raman spectra show unique signatures of the number of layers in the film. The nGL film analog of the Raman G-band in graphite exhibits a Lorentzian lineshape whose center frequency shifts linearly relative to graphite as ~1/n (f…
We investigated the thermal conductivity K of graphene ribbons and graphite slabs as the function of their lateral dimensions. Our theoretical model considered the anharmonic three-phonon processes to the second-order and included the angle-dependent phonon scattering from the ribbon edges. It was found that the long mean free path of the long-wavelength acoustic phonons in graphene can lead to an unusual non-monotonic dependence of the thermal conductivity on the length L of a ribbon. The effect is pronounced for the ribbons with the smooth edges (specularity parameter p>0.5). Our results als…
Being used in optoelectronic devices as ultra-thin conductor-insulator junctions, detailed investigations are needed about how exactly h-BN and graphene hybridize. Here, we present a comprehensive ab initio study of hot carrier dynamics governed by electron-phonon scattering at the h-BN/graphene interface, using graphite (bulk), monolayer and bilayer graphene as benchmark materials. In contrast to monolayer graphene, all multilayer structures possess low-energy optical phonon modes that facilitate carrier thermalization. We find that the h-BN/graphene interface represents an exception with com…
Taking into account the constraints imposed by the lattice symmetry, we calculate the phonon dispersion for graphene with interactions between the first, second, and third nearest neighbors in the framework of the Born--von Karman model. Analytical expressions obtained for the dispersion of the out-of-plane (bending) modes give the nonzero sound velocity. The dispersion of four in-plane modes is determined by coupled equations. Values of the force constants are found in fitting with frequencies at critical points and with elastic constants measured on graphite.
We report the results of an experimental study of thermal and magnetic properties of nanostructured ferrimagnetic iron oxide composites with graphene and graphite fillers synthesized via the current activated pressure assisted densification. The thermal conductivity was measured using the laser-flash and transient plane source techniques. It was demonstrated that addition of 5 wt. % of equal mixture of graphene and graphite flakes to the composite results in a factor of x2.6 enhancement of the thermal conductivity without significant degradation of the saturation magnetization. The microscopy …
Our low-temperature magneto-Raman scattering measurements performed on graphene-like locations on the surface of bulk graphite reveal a new series of magneto-phonon resonances involving both K-point and Gamma-point phonons. In particular, we observe for the first time the resonant splitting of three crossing excitation branches. We give a detailed theoretical analysis of these new resonances. Our results highlight the role of combined excitations and the importance of multi-phonon processes (from both K and Gamma points) for the relaxation of hot carriers in graphene.
The micro-Raman scattering response of a graphene-like location on the surface of bulk natural graphite is investigated both at $T=\unit{4.2}{K}$ and at room temperature in magnetic fields up to 29 T. Two different polarization configurations, co-circular and crossed-circular, are employed in order to determine the Raman scattering selection rules. Several distinct series of electronic excitations are observed and we discuss their characteristic shapes and amplitudes. In particular, we report a clear splitting of the signals associated with the inter-Landau level excitations $-n\rightarrow+n$.…
Taking into account the constraints imposed by the lattice symmetry, the phonon dispersion is calculated for graphene with interactions between the first and second nearest neighbors in the framework of the Born-von Karman model. Analytical expressions are obtained for the out-of-plane (bending) modes determined only by two force constants as well as for the in-plane modes with four force constants. Values of the force constants are found in fitting to elastic constants and Raman frequencies observed in graphite.
Graphene phonons are measured as a function of electron doping via the addition of potassium adatoms. In the low doping regime, the in-plane carbon G-peak hardens and narrows with increasing doping, analogous to the trend seen in graphene doped via the field-effect. At high dopings, beyond those accessible by the field-effect, the G-peak strongly softens and broadens. This is interpreted as a dynamic, non-adiabatic renormalization of the phonon self-energy. At dopings between the light and heavily doped regimes, we find a robust inhomogeneous phase where the potassium coverage is segregated in…
An algorithm for mapping the true phonon modes of a film, which are defined by a two-dimensional (2D) Brillouin zone, to the modes of the corresponding bulk material, which are defined by a three-dimensional (3D) Brillouin zone, is proposed. The algorithm is based on normal mode decomposition and is inspired by the observation that the atomic motions generated by the 2D eigenvectors lead to standing-wave-like behaviors in the cross-plane direction. It is applied to films between two and ten unit cells thick built from Lennard-Jones (LJ) argon, whose bulk is isotropic, and graphene, whose bulk …
We have examined the commonly used Tersoff and Brenner empirical interatomic potentials in the context of the phonon dispersions in graphene. We have found a parameter set for each empirical potential that provides improved fits to some structural data and to the in-plane phonon dispersion data for graphite. These optimized parameter sets yield values of the acoustic phonon velocities that are in better agreement with measured data. They also provide lattice thermal conductivity values in single-walled carbon nanotubes that are considerably improved compared to those obtained from the original…
Density functional perturbation theory is used to analyze electron-phonon interaction in bilayer graphene. The results show that phonon scattering in bilayer graphene bears more resemblance with bulk graphite than monolayer graphene. In particular, electron-phonon scattering in the lowest conduction band is dominated by six lowest (acoustic and acoustic-like) phonon branches with only minor contributions from optical modes. The total scattering rate at low/moderate electron energies can be described by a simple two-phonon model in the deformation potential approximation with effective constant…
We present the interatomic force constants and phonon dispersions of graphite and graphene from the LCBOPII empirical bond order potential. We find a good agreement with experimental results, particularly in comparison to other bond order potentials. From the flexural mode we determine the bending rigidity of graphene to be 0.69 eV at zero temperature. We discuss the large increase of this constant with temperature and argue that derivation of force constants from experimental values should take this feature into account. We examine also other graphitic systems, including multilayer graphene f…
We study the electron-phonon coupling in twisted bilayer graphene (TBG), which was recently experimentally observed to exhibit superconductivity around the magic twist angle $θ\approx 1.05^\circ$. We show that phonon-mediated electron electron attraction at the magic angle is strong enough to induce a conventional intervalley pairing between graphene valleys $K$ and $K'$ with a superconducting critical temperature $T_c\sim1K$, in agreement with the experiment. We predict that superconductivity can also be observed in TBG at many other angles $θ$ and higher electron densities in higher Moiré ba…
We use the methods of topological quantum chemistry to explore the topology of phonons on time-reversal symmetric crystals with the structure of the planar honeycomb (layer group $p6/mmm$). This approach is not tied to a particular model of atomic vibrations, but is applied to the most general dynamical matrix constrained only by the symmetries of the system. We show that four distinct fragile topological phonon phases are generically possible. Truncating the dynamical matrix to third nearest neighbors yields a model that realizes the different phonon topologies, characterized by the existence…
The sheet samples of thermally exfoliated graphite (TEG) carbon nanotubes (CNT) composites (TEG CNT cs) were obtained by persulphate oxidation using chemical (CO) and electrochemical (anode) oxidation (ECAO). Electron microscopy reveals multi layered structures of few layer graphene nanosheets with folded and tubular like fragments.Electron microscopy reveals multilayered structures of few layer graphene nanosheets with folded and tubular like fragments. The effective thermal diffusivity values were estimated by nonstationary photo-pyroelectric thermophysical characterization using the heat pu…
We make use of micro-magneto Raman scattering spectroscopy to probe magneto-phonon resonances (MPR) in suspended mono- to penta-layer graphene. MPR correspond to avoided crossings between zone-center optical phonons (G-mode) and optically-active inter Landau level (LL) transitions and provide a tool to perform LL spectroscopy at a fixed energy ($\approx 197~\rm{meV}$) set by the G-mode phonon. Using a single-particle effective bilayer model, we readily extract the velocity parameter associated with each MPR. A single velocity parameter slightly above the bulk graphite value suffices to fit all…
Properties of phonons - quanta of the crystal lattice vibrations - in graphene have attracted strong attention of the physics and engineering communities. Acoustic phonons are the main heat carriers in graphene near room temperature while optical phonons are used for counting the number of atomic planes in Raman experiments with few-layer graphene. It was shown both theoretically and experimentally that transport properties of phonons, i.e. energy dispersion and scattering rates, are substantially different in the quasi two-dimensional system such as graphene compared to basal planes in graphi…
The electronic structure of bilayer graphene is investigated from a resonant Raman study using different laser excitation energies. The values of the parameters of the Slonczewski-Weiss-McClure model for graphite are measured experimentally and some of them differ significantly from those reported previously for graphite, specially that associated with the difference of the effective mass of electrons and holes. The splitting of the two TO phonon branches in bilayer graphene is also obtained from the experimental data. Our results have implications for bilayer graphene electronic devices.
We use first-principles methods to reveal that in ZrTe$_5$, a layered van der Waals material like graphite, atomic displacements corresponding to five of the six zone-center A$_g$ (symmetry-preserving) phonon modes can drive a topological phase transition from strong to weak topological insulator with a Dirac semimetal state emerging at the transition, giving rise to a Dirac topology surface in the multi-dimensional space formed by the A$_g$ phonon modes. This implies that the topological phase transition in ZrTe$_5$ can be realized with many different settings of external stimuli that are cap…
Using the linearized Boltzmann transport equation and perturbation theory, we analyze the reduction in the intrinsic thermal conductivity of few-layer graphene sheets accounting for all possible three-phonon scattering events. Even with weak coupling between layers, a significant reduction in the thermal conductivity of the out-of-plane acoustic modes is apparent. The main effect of this weak coupling is to open many new three-phonon scattering channels that are otherwise absent in graphene. However, reflection symmetry is only weakly broken with the addition of multiple layers, and ZA phonons…
Electron tunneling spectroscopy measurements on van der Waals heterostructures consisting of metal and graphene (or graphite) electrodes separated by atomically thin hexagonal boron nitride tunnel barriers are reported. The tunneling conductance dI/dV at low voltages is relatively weak, with a strong enhancement reproducibly observed to occur at around |V| ~ 50 mV. While the weak tunneling at low energies is attributed to the absence of substantial overlap, in momentum space, of the metal and graphene Fermi surfaces, the enhancement at higher energies signals the onset of inelastic processes i…
Few-layer graphene is a layered carbon material with covalent bonding in the layers and weak van der Waals interactions between the layers. The interlayer energy is more than two orders of magnitude smaller than the intralayer one, which hinders the description of the static and dynamic properties within parameter-free electron band structure models. We overcome this difficulty by introducing two sets of matrix elements - one set for the covalent bonds in the graphene layers and another one for the van der Waals interactions between adjacent graphene layers in a tight-binding model of the band…
Thermal conductivity of homogeneous twisted stacks of graphite is found to strongly depend on the misfit angle. The underlying mechanism relies on the angle dependence of phonon-phonon couplings across the twisted interface. Excellent agreement between the calculated thermal conductivity of narrow graphitic stacks and corresponding experimental results indicates the validity of the predictions. This is attributed to the accuracy of interlayer interactions descriptions obtained by the dedicated registry-dependent interlayer potential used. Similar results for h-BN stacks indicate overall higher…
Graphene is the two-dimensional (2d) building block for carbon allotropes of every other dimensionality. It can be stacked into 3d graphite, rolled into 1d nanotubes, or wrapped into 0d fullerenes. Its recent discovery in free state has finally provided the possibility to study experimentally its electronic and phonon properties. Here we show that graphene's electronic structure is uniquely captured in its Raman spectrum that clearly evolves with increasing number of layers. Raman fingerprints for single-, bi- and few-layer graphene reflect changes in the electronic structure and electron-phon…
This is a short review of two-dimensional Dirac fermions in graphene and similar systems such as boron nitride, quasi-2D organic salts $α$-(BEDT-TTF)$_2$I$_3$, artificial graphene with cold atoms in optical lattices, etc. The emphasis is on magnetic field properties (semi-classical quantization of cyclotron orbits, Landau levels, quantum Hall effect, magneto-plasmons, magneto-phonon resonance, magneto-transport, etc.) and on topological properties (Berry phase, winding number, inter-band effects, merging transition of Dirac points, etc.).
Layered materials have uncommonly anisotropic thermal properties due to their strong in-plane covalent bonds and weak out-of-plane van der Waals interactions. Here we examine heat flow in graphene (graphite), h-BN, MoS2, and WS2 monolayers and bulk films, from diffusive to ballistic limits. We determine the ballistic thermal conductance limit (Gball) both in-plane and out-of-plane, based on full phonon dispersions from first-principles calculations. An overall phonon mean free path (λ) is expressed in terms of Gball and the diffusive thermal conductivity, consistent with kinetic theory if prop…
