Showing papers by "Francesco Mauri published in 2019"

Unified theory of thermal transport in crystals and glasses

Abstract: Crystals and glasses exhibit fundamentally different heat conduction mechanisms: the periodicity of crystals allows for the excitation of propagating vibrational waves that carry heat, as first discussed by Peierls, while in glasses the lack of periodicity breaks Peierls’s picture and heat is mainly carried by the coupling of vibrational modes, often described by a harmonic theory introduced by Allen and Feldman. Anharmonicity or disorder are thus the limiting factors for thermal conductivity in crystals or glasses. Hitherto, no transport equation has been able to account for both. Here, we derive such an equation, resulting in a thermal conductivity that reduces to the Peierls and Allen–Feldman limits, respectively, in anharmonic crystals or harmonic glasses, while also covering the intermediate regimes where both effects are relevant. This approach also solves the long-standing problem of accurately predicting the thermal properties of crystals with ultralow or glass-like thermal conductivity, as we show with an application to a thermoelectric material representative of this class. A unified theory for the conduction of heat in materials is derived and shown to account for both the limiting regimes of periodic crystals and aperiodic glasses.

Unified theory of thermal transport in crystals and disordered solids

Abstract: Crystals and glasses exhibit fundamentally different heat conduction mechanisms: the periodicity of crystals allows for the excitation of propagating vibrational waves that carry heat, as first discussed by Peierls; in glasses, the lack of periodicity breaks Peierls' picture and heat is mainly carried by the coupling of vibrational modes, often described by a harmonic theory introduced by Allen and Feldman. Anharmonicity or disorder are thus the limiting factors for thermal conductivity in crystals or glasses; hitherto, no transport equation has been able to account for both. Here, we derive such equation, resulting in a thermal conductivity that reduces to the Peierls and Allen-Feldman limits, respectively, in anharmonic-and-ordered or harmonic-and-disordered solids, while also covering the intermediate regimes where both effects are relevant. This approach also solves the long-standing problem of accurately predicting the thermal properties of crystals with ultralow or glass-like thermal conductivity, as we show with an application to a thermoelectric material representative of this class.

Quantum Crystal Structure in the 250 K Superconducting Lanthanum Hydride

Abstract: The discovery of superconductivity at 200 K in the hydrogen sulfide system at large pressures [1] was a clear demonstration that hydrogen-rich materials can be high-temperature superconductors. The recent synthesis of LaH$_{10}$ with a superconducting critical temperature (T$_{\text{c}}$) of 250 K [2,3] places these materials at the verge of reaching the long-dreamed room-temperature superconductivity. Electrical and x-ray diffraction measurements determined a weakly pressure-dependent T$_{\text{c}}$ for LaH$_{10}$ between 137 and 218 gigapascals in a structure with a face-centered cubic (fcc) arrangement of La atoms [3]. Here we show that quantum atomic fluctuations stabilize in all this pressure range a high-symmetry Fm-3m crystal structure consistent with experiments, which has a colossal electron-phonon coupling of $\lambda\sim3.5$. Even if ab initio classical calculations neglecting quantum atomic vibrations predict this structure to distort below 230 GPa yielding a complex energy landscape with many local minima, the inclusion of quantum effects simplifies the energy landscape evidencing the Fm-3m as the true ground state. The agreement between the calculated and experimental T$_{\text{c}}$ values further supports this phase as responsible for the 250 K superconductivity. The relevance of quantum fluctuations in the energy landscape found here questions many of the crystal structure predictions made for hydrides within a classical approach that at the moment guide the experimental quest for room-temperature superconductivity [4,5,6]. Furthermore, quantum effects reveal crucial to sustain solids with extraordinary electron-phonon coupling that may otherwise be unstable [7].

Phonon Collapse and Second-Order Phase Transition in Thermoelectric SnSe.

Abstract: Since 2014 the layered semiconductor SnSe in the high-temperature $Cmcm$ phase is known to be the most efficient intrinsic thermoelectric material Making use of first-principles calculations we show that its vibrational and thermal transport properties are determined by huge nonperturbative anharmonic effects We show that the transition from the $Cmcm$ phase to the low-symmetry $Pnma$ is a second-order phase transition driven by the collapse of a zone border phonon, whose frequency vanishes at the transition temperature Our calculations show that the spectral function of the in-plane vibrational modes are strongly anomalous with shoulders and double-peak structures We calculate the lattice thermal conductivity obtaining good agreement with experiments only when nonperturbative anharmonic scattering is included Our results suggest that the good thermoelectric efficiency of SnSe is strongly affected by the nonperturbative anharmonicity

Optomechanical Measurement of Thermal Transport in Two-Dimensional MoSe2 Lattices

Abstract: Nanomechanical resonators have emerged as sensors with exceptional sensitivities. These sensing capabilities open new possibilities in the studies of the thermodynamic properties in condensed matter. Here, we use mechanical sensing as a novel approach to measure the thermal properties of low-dimensional materials. We measure the temperature dependence of both the thermal conductivity and the specific heat capacity of a transition metal dichalcogenide monolayer down to cryogenic temperature, something that has not been achieved thus far with a single nanoscale object. These measurements show how heat is transported by phonons in two-dimensional systems. Both the thermal conductivity and the specific heat capacity measurements are consistent with predictions based on first-principles.

Position and momentum mapping of vibrations in graphene nanostructures

Abstract: Propagating atomic vibrational waves—phonons—determine important thermal, mechanical, optoelectronic and transport characteristics of materials. Thus a knowledge of phonon dispersion (that is, the dependence of vibrational energy on momentum) is a key part of our understanding and optimization of a material’s behaviour. However, the phonon dispersion of a free-standing monolayer of a two-dimensional material such as graphene, and its local variations, have remained elusive for the past decade because of the experimental limitations of vibrational spectroscopy. Even though electron energy loss spectroscopy (EELS) in transmission has recently been shown to probe local vibrational charge responses1–4, such studies are still limited by momentum space integration due to the focused beam geometry; they are also restricted to polar materials such as boron nitride or oxides1–4, in which huge signals induced by strong dipole moments are present. On the other hand, measurements on graphene performed by inelastic X-ray (neutron) scattering spectroscopy5–7 or EELS in reflection8,9 do not have any spatial resolution and require large microcrystals. Here we provide a new pathway to determine phonon dispersions down to the scale of an individual free-standing graphene monolayer by mapping the distinct vibrational modes for a large momentum transfer. The measured scattering intensities are accurately reproduced and interpreted with density functional perturbation theory10. Additionally, a nanometre-scale mapping of selected momentum-resolved vibrational modes using graphene nanoribbon structures has enabled us to spatially disentangle bulk, edge and surface vibrations. Our results are a proof-of-principle demonstration of the feasibility of studying local vibrational modes in two-dimensional monolayer materials at the nanometre scale. Investigation of a free-standing graphene monolayer using a technique based on transmission electron microscopy allows identification of atomic vibrations characteristic of the bulk or the edge of the sample.

Quantum Enhancement of Charge Density Wave in NbS2 in the Two-Dimensional Limit.

Abstract: At ambient pressure, bulk 2H-NbS2 displays no charge density wave instability, which is at odds with the isostructural and isoelectronic compounds 2H-NbSe2, 2H-TaS2, and 2H-TaSe2, and in disagreement with harmonic calculations. Contradictory experimental results have been reported in supported single layers, as 1H-NbS2 on Au(111) does not display a charge density wave, whereas 1H-NbS2 on 6H-SiC(0001) endures a 3 × 3 reconstruction. Here, by carrying out quantum anharmonic calculations from first-principles, we evaluate the temperature dependence of phonon spectra in NbS2 bulk and single layer as a function of pressure/strain. For bulk 2H-NbS2, we find excellent agreement with inelastic X-ray spectra and demonstrate the removal of charge ordering due to anharmonicity. In the two-dimensional limit, we find an enhanced tendency toward charge density wave order. Freestanding 1H-NbS2 undergoes a 3 × 3 reconstruction, in agreement with data on 6H-SiC(0001) supported samples. Moreover, as strains smaller than 0.5% in the lattice parameter are enough to completely remove the 3 × 3 superstructure, deposition of 1H-NbS2 on flexible substrates or a small charge transfer via field-effect could lead to devices with dynamical switching on/off of charge order.

Strong anharmonicity and high thermoelectric efficiency in high-temperature SnS from first principles

Abstract: SnS and SnSe are isoelectronic materials with a common phase diagram. Recently, SnSe was found to be the most efficient intrinsic thermoelectric material in its high-temperature $Cmcm$ phase above 800 K. Making use of first-principles calculations, here we show that the electronic and vibrational properties of both materials are very similar in this phase and, consequently, SnS is also expected to have a high thermoelectric figure of merit at high temperature in its $Cmcm$ phase. In fact, the electronic power factor and lattice thermal conductivity are comparable for both materials, which ensures a similar figure of merit. As in the case of SnSe, the vibrational properties of SnS in the $Cmcm$ phase are far from trivial and are dominated by huge anharmonic effects. Its phonon spectra are strongly renormalized by anharmonicity and the spectral functions of some particular in-plane modes depict anomalous non-Lorentzian profiles. Finally, we show that nonperturbative anharmonic effects in the third-order force-constants are crucial in the calculation of the lattice thermal conductivity. Our results motivate new experiments in the high-temperature regime to measure the figure of merit of SnS.

Giant effective charges and piezoelectricity in gapped graphene

Abstract: Since the first realization of reversible charge doping in graphene via field-effect devices, it has become evident how the induction a gap could further enhance its potential for technological applications. Here we show that the gap opening due to a sublattice symmetry breaking has also a profound impact on the polar response of graphene. By combining ab-initio calculations and analytical modelling we show that for realistic band-gap values ($\Delta\lesssim 0.5$ eV) the piezoelectric coefficient and the Born effective charge of graphene attain a giant value, independent on the gap. In particular the piezoelectric coefficient per layer of gapped mono- and bilayer graphene is three times larger than that of a large-gap full polar insulator as hexagonal Boron Nitride (h-BN) monolayer, and 30\% larger than that of a polar semiconductor as MoS$_2$. This surprising result indicates that piezoelectric acoustic-phonons scattering can be relevant to model charge transport and charge-carrier relaxation in gated bilayer graphene. The independence of the piezoelectric coefficient and of the Born effective charge on the gap value follows from the connection between the polar response and the valley Chern number of gapped Dirac electrons, made possible by the effective gauge-field description of the electron-lattice/strain coupling in these systems. In the small gap limit, where the adiabatic ab-initio approximation fails, we implement analytically the calculation of the dynamical effective charge, and we establish a universal relation between the complex effective charge and the so-called Fano profile of the phonon optical peak. Our results provide a general theoretical framework to understand and compute the polar response in narrow-gap semiconductors, but may also be relevant for the contribution of piezoelectric scattering to the transport properties in Dirac-like systems.

Quantum effects in muon spin spectroscopy within the stochastic self-consistent harmonic approximation

Abstract: RDR acknowledges grants from the European Union’s Horizon 2020 research and innovation program under Grant Agreement No. 654000. RDR, PB and IJO also acknowledge computing resources provided by, the Swiss National Supercomputing Centre (CSCS) under Project ID sm16, CINECA under Project ID IsC58, the STFC Scientific Computing Departments SCARF cluster and the HPC resources at the University of Parma, Italy. IE acknowledges funding from the Spanish Ministry of Economy and Competitiveness (FIS2016-76617-P). This work is part of the PhD thesis of IJO at the University of Parma, Italy

Quantum enhancement of charge density wave in NbS2 in the 2D limit

Abstract: I.E. acknowledges financial support from the Spanish Ministry of Economy and Competitiveness (Grant No. FIS2016- 76617-P). M.C. acknowledges support from Agence Nationale de la Recherche under the reference No. ANR13-IS10-0003- 01. We acknowledge support from the Graphene Flagship (Grant Agreement No. 696656- GrapheneCore1).

Extraordinary high room-temperature carrier mobility in graphene-WSe$_2$ heterostructures

Abstract: High carrier mobilities play a fundamental role for high-frequency electronics, integrated optoelectronics as well as for sensor and spintronic applications, where device performance is directly linked to the magnitude of the carrier mobility. Van der Waals heterostructures formed by graphene and hexagonal boron nitride (hBN) already outperform all known materials in terms of room temperature mobility. Here, we show that the mobility of today's best graphene/hBN devices can be surpassed by more than a factor of three by heterostructures formed by tungsten diselenide (WSe$_2$), graphene and hBN, which can have mobilities as high as 350,000 cm$^2$/(Vs) at room temperature, and resistivities as low as 15 Ohm. The resistivity of these devices shows a much weaker temperature dependence than the one of graphene on any other known substrate. The origin of this behaviour points to modified acoustic phonon bands in graphene and questions our understanding of electron-phonon scattering in van der Waals heterostructures.

van der Waals forces stabilize low-energy polymorphism in B2O3: Implications for the crystallization anomaly

Abstract: The cohesive energies and structural properties of recently predicted, and never synthesized, B$_2$O$_3$ polymorphs are investigated from first principles using density functional theory and high-accuracy many-body methods, namely, the random phase approximation and quantum Monte Carlo. We demonstrate that the van der Waals forces play a key role in making the experimentally known polymorph (B$_2$O$_3$-I) the lowest in energy, with many competing metastable structures lying only a few kcal/mol above. Remarkably, all metastable crystals are comparable in energy and density to the glass, while having anisotropic and mechanically soft structures. Furthermore, the best metastable polymorph according to our stability criteria has a structural motif found in both the glass and a recently synthesized borosulfate compound. Our findings provide new perspectives for understanding the B$_2$O$_3$ anomalous behavior, namely, its propensity to vitrify in a glassy structure drastically different from the known crystal.

Gate Tunable Magnetism and Giant Magnetoresistance in ABC-stacked Few-Layer Graphene

Abstract: Magnetism is a prototypical phenomenon of quantum collective state, and has found ubiquitous applications in semiconductor technologies such as dynamic random access memory (DRAM). In conventional materials, it typically arises from the strong exchange interaction among the magnetic moments of d- or f-shell electrons. Magnetism, however, can also emerge in perfect lattices from non-magnetic elements. For instance, flat band systems with high density of states (DOS) may develop spontaneous magnetic ordering, as exemplified by the Stoner criterion. Here we report tunable magnetism in rhombohedral-stacked few-layer graphene (r-FLG). At small but finite doping (n~10^11 cm-2), we observe prominent conductance hysteresis and giant magnetoconductance that exceeds 1000% as a function of magnetic fields. Both phenomena are tunable by density and temperature, and disappears for n>10^12 cm-2 or T>5K. These results are confirmed by first principles calculations, which indicate the formation of a half-metallic state in doped r-FLG, in which the magnetization is tunable by electric field. Our combined experimental and theoretical work demonstrate that magnetism and spin polarization, arising from the strong electronic interactions in flat bands, emerge in a system composed entirely of carbon atoms. The electric field tunability of magnetism provides promise for spintronics and low energy device engineering.

van der Waals forces stabilize low-energy polymorphism in B 2 O 3 : Implications for the crystallization anomaly

Abstract: The cohesive energies and structural properties of recently predicted, and never synthesized, ${\mathrm{B}}_{2}{\mathrm{O}}_{3}$ polymorphs are investigated from first principles using density functional theory and high-accuracy many-body methods, namely, the random phase approximation and quantum Monte Carlo. We demonstrate that the van der Waals forces play a key role in making the experimentally known polymorph (${\mathrm{B}}_{2}{\mathrm{O}}_{3}\text{\ensuremath{-}}\mathrm{I}$) the lowest in energy, with many competing metastable structures lying only a few kcal/mol above. Remarkably, all metastable crystals are comparable in energy and density to the glass, while having anisotropic and mechanically soft structures. Furthermore, the best metastable polymorph according to our stability criteria has a structural motif found in both the glass and a recently synthesized borosulfate compound. Our findings provide a framework for understanding the ${\mathrm{B}}_{2}{\mathrm{O}}_{3}$ anomalous behavior, namely, its propensity to vitrify in a glassy structure drastically different from the known crystal.

Black metal hydrogen above 360 GPa driven by proton quantum fluctuations

Abstract: Production of metallic hydrogen is one of the top three open quests of physics. Recent low-temperature experiments report different metallization pressures, varying from 360GPa to 490GPa. In this work, we simulate structural properties, vibrational Raman, IR and optical spectra of hydrogen phase III accounting for proton quantum effects. We demonstrate that nuclear quantum fluctuations downshift the vibron frequencies by 25%, introduce a broad line-shape in the Raman spectra, and reduce the optical gap by 3eV. We show that hydrogen metallization occurs at 380GPa in phase III due to band overlap, in good agreement with transport data. By simulating the optical properties, we predict this state to be a peculiar black metal, transparent in the IR. The transparent window closes at 450GPa, but the reflectivity remains low, discarding phase III as the shiny metal observed at 490GPa. We predict the conductivity onset to increase by 70GPa and the transparent window to increase by 1.3eV when replacing hydrogen by deuterium at 0K, underlining that metallization is driven by quantum fluctuations and is thus isotope dependent. We show how hydrogen acquires metallic features (conductivity and brightness) at different pressures, explaining the apparent contradictions in existing experimental scenarios.

Giant Effective charges and Piezoelectricity in Gapped Graphene.

Abstract: Since the first realization of reversible charge doping in graphene via field-effect devices, it has become evident how the induction a gap could further enhance its potential for technological applications. Here we show that the gap opening due to a sublattice symmetry breaking has also a profound impact on the polar response of graphene. By combining ab-initio calculations and analytical modelling we show that for realistic band-gap values ($\Delta\lesssim 0.5$ eV) the piezoelectric coefficient and the Born effective charge of graphene attain a giant value, independent on the gap. In particular the piezoelectric coefficient per layer of gapped mono- and bilayer graphene is three times larger than that of a large-gap full polar insulator as hexagonal Boron Nitride (h-BN) monolayer, and 30\% larger than that of a polar semiconductor as MoS$_2$. This surprising result indicates that piezoelectric acoustic-phonons scattering can be relevant to model charge transport and charge-carrier relaxation in gated bilayer graphene. The independence of the piezoelectric coefficient and of the Born effective charge on the gap value follows from the connection between the polar response and the valley Chern number of gapped Dirac electrons, made possible by the effective gauge-field description of the electron-lattice/strain coupling in these systems. In the small gap limit, where the adiabatic ab-initio approximation fails, we implement analytically the calculation of the dynamical effective charge, and we establish a universal relation between the complex effective charge and the so-called Fano profile of the phonon optical peak. Our results provide a general theoretical framework to understand and compute the polar response in narrow-gap semiconductors, but may also be relevant for the contribution of piezoelectric scattering to the transport properties in Dirac-like systems.

Anharmonic melting of the charge density wave in single-layer TiSe2

Abstract: Low dimensional systems with a vanishing band-gap and a large electron-hole interaction have been proposed to be unstable towards exciton formation. As the exciton binding energy increases in low dimension, conventional wisdom suggests that excitonic insulators should be more stable in 2D than in 3D. Here we study the effects of the electron-hole interaction and anharmonicity in single-layer TiSe2. We find that, contrary to the bulk case and to the generally accepted picture, the electron-hole exchange interaction is much smaller in 2D than in 3D and it has negligible effects on phonon spectra. By calculating anharmonic phonon spectra within the stochastic self-consistent harmonic approximation, we obtain TCDW = 440K for an isolated and undoped single-layer and TCDW = 364K for an electron-doping n = 4.6 x 10^13 cm^{-2} , close to the experimental result of 200-280K on supported samples. Our work demonstrates that anharmonicity and doping melt the charge density wave in single-layer TiSe2.

Raman spectroscopy of graphene under ultrafast laser excitation

Abstract: The out-of-equilibrium Raman response of graphene is addressed by pulsed laser excitation. Phonon spectrum is rationalized by revisiting the electron-phonon picture in the light of a transient broadening of the Dirac cone.

Unified theory of thermal transport in crystals and disordered solids

Abstract: Crystals and glasses exhibit fundamentally different heat conduction mechanisms: the periodicity of crystals allows for the excitation of propagating vibrational waves that carry heat, as first discussed by Peierls; in glasses, the lack of periodicity breaks Peierls' picture and heat is mainly carried by the coupling of vibrational modes, often described by a harmonic theory introduced by Allen and Feldman. Anharmonicity or disorder are thus the limiting factors for thermal conductivity in crystals or glasses; hitherto, no transport equation has been able to account for both. In the paper https://arxiv.org/abs/1901.01964, we derive such equation, resulting in a thermal conductivity that reduces to the Peierls and Allen-Feldman limits, respectively, in anharmonic-and-ordered or harmonic-and-disordered solids, while also covering the intermediate regimes where both effects are relevant. This approach also solves the long-standing problem of accurately predicting the thermal properties of crystals with ultralow or glass-like thermal conductivity, as we show with an application to a thermoelectric material representative of this class. This database contains the raw data related to the images reported in the paper https://arxiv.org/abs/1901.01964.

Quantum effects in muon spin spectroscopy within the stochastic self-consistent harmonic approximation

Abstract: In muon spin rotation experiments the positive implanted muon vibrates with large zero point amplitude by virtue of its light mass. Quantum mechanical calculations of the host material usually treat the muon as a point impurity, ignoring this large vibrational amplitude. As a first order correction, the muon zero point motion is usually described within the harmonic approximation, despite the large anharmonicity of the crystal potential. Here we apply the stochastic self-consistent harmonic approximation, a quantum variational method devised to include strong anharmonic effects in total energy and vibrational frequency calculations, in order to overcome these limitations and provide an accurate ab initio description of the quantum nature of the muon. We applied this full quantum treatment to the calculation of the muon contact hyperfine field in textbook-case metallic systems, such as Fe, Ni, Co including MnSi and MnGe, significantly improving agreement with experiments. Our results show that muon vibrational frequencies are strongly renormalized by anharmonicity. Finally, in contrast to the harmonic approximation, we show that including quantum anharmonic fluctuations, the muon stabilizes at the octahedral site in bcc Fe.

Nanoscale Vibrational Spectroscopy of Graphene by Large-q EELS

Abstract: Since all low-energy quasiparticle excitations are strongly coupled to phonons governing their unique properties, a full description of phonon dispersion is of paramount importance to explore the physical properties of low-dimensional materials. However, existing techniques lack the complementary resolutions in spatial-, energy-, and momentum-space required to measure phonon dispersions in nanoscale. For instance, material phonon dispersions have been usually drawn by inelastic x-ray (neutron) scattering spectroscopy or electron energy loss spectroscopy (EELS) in reflection. Although these techniques have sufficiently high momentum (~0.01 Å) and energy resolution (~1 meV) to figuratively complete phonon dispersion, measurable objects are basically in the micrometer to millimeter scale with a few hundreds of nanometer thickness. Thus, all local information, such as phonon scatterings at non-perfect structures, is averaged in a spectrum.