Nature of Hexagonal Silicon Forming via High-Pressure Synthesis: Nanostructured Hexagonal 4H Polytype.

Hexagonal Si allotropes are expected to enhance light absorption in the visible range as compared to common cubic Si with diamond structure. Therefore, synthesis of these materials is crucial for the development of Si-based optoelectronics. In this work, we combine in situ high-pressure high-temperature synthesis and vacuum heating to obtain hexagonal Si. High pressure is one of the most promising routes to stabilize these allotropes. It allows one to obtain large-volume nanostructured ingots by a sequence of direct solid-solid transformations, ensuring high-purity samples for detailed characterization. Thanks to our synthesis approach, we provide the first evidence of a polycrystalline bulk sample of hexagonal Si. Exhaustive structural analysis, combining fine-powder X-ray and electron diffraction, afforded resolution of the crystal structure. We demonstrate that hexagonal Si obtained by high-pressure synthesis correspond to Si-4H polytype (ABCB stacking) in contrast with Si-2H (AB stacking) proposed previously. This result agrees with prior calculations that predicted a higher stability of the 4H form over 2H form. Further physical characterization, combining experimental data and ab initio calculations, have shown a good agreement with the established structure. Strong photoluminescence emission was observed in the visible region for which we foresee optimistic perspectives for the use of this material in Si-based photovoltaics.

Hydrodynamic Heat Transport Regime in Bismuth: A Theoretical Viewpoint.

Bismuth is one of the rare materials in which second sound has been experimentally observed. Our exact calculations of thermal transport with the Boltzmann equation predict the occurrence of this Poiseuille phonon flow between ≈1.5 and ≈3.5 K, in a sample size of 3.86 and 9.06 mm, consistent with the experimental observations. Hydrodynamic heat flow characteristics are given for any temperature: heat wave propagation length, drift velocity, and Knudsen number. We discuss a gedanken experiment allowing us to assess the presence of a hydrodynamic regime in any bulk material.

Temperature dependence of X-ray absorption and nuclear magnetic resonance spectra: probing quantum vibrations of light elements in oxides.

A combined experimental-theoretical study on the temperature dependence of the X-ray absorption near-edge structure (XANES) and nuclear magnetic resonance (NMR) spectra of periclase (MgO), spinel (MgAl2O4), corundum (α-Al2O3), berlinite (α-AlPO4), stishovite and α-quartz (SiO2) is reported. Predictive calculations are presented when experimental data are not available. For these light-element oxides, both experimental techniques detect systematic effects related to quantum thermal vibrations which are well reproduced by density-functional theory simulations. In calculations, thermal fluctuations of the nuclei are included by considering nonequilibrium configurations according to finite-temperature quantum statistics at the quasiharmonic level. The influence of nuclear quantum fluctuations on XANES and NMR spectroscopies is particularly sensitive to the coordination number of the probed cation. Furthermore, the relative importance of nuclear dynamics and thermal expansion is quantified over a large range of temperatures.

Thermal conductivity of graphene and graphite: collective excitations and mean free paths.

We characterize the thermal conductivity of graphite, monolayer graphene, graphane, fluorographane, and bilayer graphene, solving exactly the Boltzmann transport equation for phonons, with phonon-phonon collision rates obtained from density functional perturbation theory. For graphite, the results are found to be in excellent agreement with experiments; notably, the thermal conductivity is 1 order of magnitude larger than what found by solving the Boltzmann equation in the single mode approximation, commonly used to describe heat transport. For graphene, we point out that a meaningful value of intrinsic thermal conductivity at room temperature can be obtained only for sample sizes of the order of 1 mm, something not considered previously. This unusual requirement is because collective phonon excitations, and not single phonons, are the main heat carriers in these materials; these excitations are characterized by mean free paths of the order of hundreds of micrometers. As a result, even Fourier's law becomes questionable in typical sample sizes, because its statistical nature makes it applicable only in the thermodynamic limit to systems larger than a few mean free paths. Finally, we discuss the effects of isotopic disorder, strain, and chemical functionalization on thermal performance. Only chemical functionalization is found to play an important role, decreasing the conductivity by a factor of 2 in hydrogenated graphene, and by 1 order of magnitude in fluorogenated graphene.

Two-dimensional analysis of the double-resonant 2D Raman mode in bilayer graphene.

By computing the double-resonant Raman scattering cross section completely from first principles and including the electron-electron interaction at the GW level, we unravel the dominant contributions for the double-resonant 2D mode in bilayer graphene. We show that, in contrast to previous works, the so-called inner processes are dominant and that the 2D-mode line shape is described by three dominant resonances around the K point. We show that the splitting of the transversal optical (TO) phonon branch in the Γ-K direction, as large as 12 cm(-1) in the GW approximation, is of great importance for a thorough description of the 2D-mode line shape. Finally, we present a method to extract the TO phonon splitting and the splitting of the electronic bands from experimental data.

Raman fingerprint of aligned graphene/h-BN superlattices.

Graphene placed on hexagonal-boron nitride (h-BN) experiences a superlattice (Moiré) potential, which leads to a strong reconstruction of graphene's electronic spectrum with new Dirac points emerging at sub-eV energies. Here we study the effect of such superlattices on graphene's Raman spectrum. In particular, the 2D Raman peak is found to be exquisitely sensitive to the misalignment between graphene and h-BN lattices, probably due to the presence of a strain distribution with the same periodicity of the Moiré potential. This feature can be used to identify graphene superlattices with a misalignment angle smaller than 2°.

Hidden polymorphs drive vitrification in B2O3.

Understanding the conditions that favour crystallization or vitrification of liquids has been a long-standing scientific problem. Another connected, and not yet well understood question is the relationship between the glassy and the various possible crystalline forms a system may adopt. In this context, B(2)O(3) represents a puzzling case. It is one of the best glass-forming systems despite an apparent lack of low-pressure polymorphism. Furthermore, the system vitrifies in a glassy form abnormally different from the only known crystalline phase at ambient pressure. Last but not least, it never crystallizes from the melt unless pressure is applied, an intriguing behaviour known as the crystallization anomaly. Here, by means of ab initio calculations, we discover the existence of previously unknown B(2)O(3) crystalline polymorphs with structural properties similar to the glass and formation energies comparable to the known ambient crystal. The energy degeneracy of the crystals, which is high at ambient pressure and suppressed under pressure, provides a framework to understand the system's ability to vitrify and the origin of the crystallization anomaly. This work reconciles the behaviour of B(2)O(3) with that from other glassy systems and reaffirms the role played by polymorphism in a system's ability to vitrify. Some of the predicted crystals are cage-like materials entirely made of three-fold rings, opening new perspectives for the synthesis of boron-based nanoporous materials.

Anisotropic Thermal Conductivity of Inkjet-Printed 2D Crystal Films: Role of the Microstructure and Interfaces.

Two-dimensional (2D) materials are uniquely suited for highly anisotropic thermal transport, which is important in thermoelectrics, thermal barrier coatings, and heat spreaders. Solution-processed 2D materials are attractive for simple, low-cost, and large-scale fabrication of devices on, virtually, any substrate. However, to date, there are only few reports with contrasting results on the thermal conductivity of graphene films, while thermal transport has been hardly measured for other types of solution-processed 2D material films. In this work, inkjet-printed graphene, h-BN and MoS2 films are demonstrated with thermal conductivities of ∼10 Wm-1K-1 and ∼0.3 Wm-1K-1 along and across the basal plane, respectively, giving rise to an anisotropy of ∼30, hardly dependent on the material type and annealing treatment. First-principles calculations indicate that portion of the phonon spectrum is cut-off by the quality of the thermal contact for transport along the plane, yet the ultra-low conductivity across the plane is associated with high-transmissivity interfaces. These findings can drive the design of highly anisotropic 2D material films for heat management applications.

Doped graphene as tunable electron-phonon coupling material.

We present a new way to tune the electron-phonon coupling (EPC) in graphene by changing the deformation potential with electron/hole doping. We show the EPC for highest optical branch at the high symmetry point K acquires a strong dependency on the doping level due to electron-electron correlation not accounted in mean-field approaches. Such a dependency influences the dispersion (with respect to the laser energy) of the Raman D and 2D lines and the splitting of the 2D peak in multilayer graphene. Finally this doping dependence opens the possibility to construct tunable electronic devices through external control of the EPC.

Clar's theory, pi-electron distribution, and geometry of graphene nanoribbons.

We show that Clar's theory of the aromatic sextet is a simple and powerful tool to predict the stability, the pi-electron distribution, the geometry, and the electronic/magnetic structure of graphene nanoribbons with different hydrogen edge terminations. We use density functional theory to obtain the equilibrium atomic positions, simulated scanning tunneling microscopy (STM) images, edge energies, band gaps, and edge-induced strains of graphene ribbons that we analyze in terms of Clar formulas. On the basis of their Clar representation, we propose a classification scheme for graphene ribbons that groups configurations with similar bond length alternations, STM patterns, and Raman spectra. Our simulations show how STM images and Raman spectra can be used to identify the type of edge termination.

High-field transport in graphene: the impact of Zener tunneling.

We study, theoretically, the impact of Zener tunneling (the generation of electron-hole pairs by the electric field) on the charge-transport properties of graphene in the high-field regime. We model Zener tunneling in a rigorous way, using the quantum master equation for the density matrix. In the presence of Zener tunneling, a steady-state can be reached only by further including an efficient mechanism for the electron thermalization such as electron-electron scattering. We treat the effects of electron-electron relaxation within a simplified model, that assumes an instantaneous separate thermalization of the electrons in the conduction band and of the holes in the valence band. The inclusion of both Zener tunneling and electron-electron relaxation improves the agreement with measurements performed in graphene in the high-field regime at low doping.

Phonon hydrodynamics in two-dimensional materials.

The conduction of heat in two dimensions displays a wealth of fascinating phenomena of key relevance to the scientific understanding and technological applications of graphene and related materials. Here, we use density-functional perturbation theory and an exact, variational solution of the Boltzmann transport equation to study fully from first-principles phonon transport and heat conductivity in graphene, boron nitride, molybdenum disulphide and the functionalized derivatives graphane and fluorographene. In all these materials, and at variance with typical three-dimensional solids, normal processes keep dominating over Umklapp scattering well-above cryogenic conditions, extending to room temperature and more. As a result, novel regimes emerge, with Poiseuille and Ziman hydrodynamics, hitherto typically confined to ultra-low temperatures, characterizing transport at ordinary conditions. Most remarkably, several of these two-dimensional materials admit wave-like heat diffusion, with second sound present at room temperature and above in graphene, boron nitride and graphane.

Boosting electronic transport in carbon nanotubes by isotopic disorder.

The current-voltage curve of metallic carbon nanotubes (CNTs) displays at high bias a sudden increase of the resistivity due to the scattering of electrons with phonons having an anomalously high population (hot phonons). Here, we show that it is possible to improve the electrical performances of metallic CNTs by 13C isotope enrichment. In fact, isotopic disorder creates additional channels for the hot-phonon deexcitation, reduces their population and, thus, the nanotube high-bias differential resistance. This is an extraordinary case where disorder improves the electronic transport.

Transport properties of graphene in the high-current limit.

We present a detailed study of the high-current transport properties of graphene devices patterned in a four-point configuration. The current tends to saturate as the voltage across graphene is increased but never reaches the complete saturation as in metallic nanotubes. Measurements are compared to a model based on the Boltzmann equation, which includes electron-scattering processes due to charged and neutral impurities, and graphene optical phonons. The saturation is incomplete because of the competition between disorder and optical phonon scattering.

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials.

QUANTUM ESPRESSO is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density-functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave). The acronym ESPRESSO stands for opEn Source Package for Research in Electronic Structure, Simulation, and Optimization. It is freely available to researchers around the world under the terms of the GNU General Public License. QUANTUM ESPRESSO builds upon newly-restructured electronic-structure codes that have been developed and tested by some of the original authors of novel electronic-structure algorithms and applied in the last twenty years by some of the leading materials modeling groups worldwide. Innovation and efficiency are still its main focus, with special attention paid to massively parallel architectures, and a great effort being devoted to user friendliness. QUANTUM ESPRESSO is evolving towards a distribution of independent and interoperable codes in the spirit of an open-source project, where researchers active in the field of electronic-structure calculations are encouraged to participate in the project by contributing their own codes or by implementing their own ideas into existing codes.

Giant nonadiabatic effects in layer metals: raman spectra of intercalated graphite explained.

The occurrence of nonadiabatic effects in the vibrational properties of metals has been predicted since the 1960s, but hardly confirmed experimentally. We report the first fully ab initio calculations of nonadiabatic frequencies of a number of conventional (hcp Ti and Mg) and layered metals (MgB2, CaC6, and other intercalated graphites). Nonadiabatic effects can be spectacularly large (up to 30% of the phonon frequencies) in both cases, but they can only be experimentally observed in the Raman spectra of layered compounds. In layered metals nonadiabatic effects are crucial to explaining the observed Raman shifts and linewidths. Moreover, we show that those quantities can be used to extract the electron momentum-relaxation time.

Boroxol Rings in Liquid and Vitreous B2O3 from First Principles.

We investigate the structural and vibrational properties of glassy B2O3 using first-principles molecular dynamics simulations. In particular, we determine the boroxol rings fraction f for which there is still no consensus in the literature. Two numerical models containing either a low or a high level of boroxol rings are tested against a gamut of experimental probes (static structure factor, Raman, 11B and 17O NMR data). We show that only the boroxol-rich model (f=75%) can reproduce the full set of observables. Total-energy calculations show that at the glass density, boroxol-rich structures are favored by about 6 kcal/(mol boroxol). Finally, the liquid state is explored in the 2,000-4,000 K range and a reduction of f to 10%-20% is obtained.

Structure, stability, edge states, and aromaticity of graphene ribbons.

We determine the stability, the geometry, the electronic, and magnetic structure of hydrogen-terminated graphene-nanoribbon edges as a function of the hydrogen content of the environment by means of density functional theory. Antiferromagnetic zigzag ribbons are stable only at extremely low ultravacuum pressures. Under more standard conditions, the most stable structures are the mono- and dihydrogenated armchair edges and a zigzag edge reconstruction with one di- and two monohydrogenated sites. At high hydrogen concentration "bulk" graphene is not stable and spontaneously breaks to form ribbons, in analogy to the spontaneous breaking of graphene into small-width nanoribbons observed experimentally in solution. The stability and the existence of exotic edge electronic states and/or magnetism is rationalized in terms of simple concepts from organic chemistry (Clar's rule).

Phonon anharmonicities in graphite and graphene.

We determine from first principles the finite-temperature properties-linewidths, line shifts, and lifetimes-of the key vibrational modes that dominate inelastic losses in graphitic materials. In graphite, the phonon linewidth of the Raman-active E(2g) mode is found to decrease with temperature; such anomalous behavior is driven entirely by electron-phonon interactions, and does not appear in the nearly degenerate infrared-active E(1u) mode. In graphene, the phonon anharmonic lifetimes and decay channels of the A(1)' mode at K dominate over E(2g) at Gamma and couple strongly with acoustic phonons, highlighting how ballistic transport in carbon-based interconnects requires careful engineering of phonon decays and thermalization.

Breakdown of the adiabatic Born-Oppenheimer approximation in graphene.

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.