Davide Campi

Two-dimensional materials from high-throughput computational exfoliation of experimentally known compounds

Two-dimensional (2D) materials have emerged as promising candidates for next-generation electronic and optoelectronic applications. Yet, only a few dozen 2D materials have been successfully synthesized or exfoliated. Here, we search for 2D materials that can be easily exfoliated from their parent compounds. Starting from 108,423 unique, experimentally known 3D compounds, we identify a subset of 5,619 compounds that appear layered according to robust geometric and bonding criteria. High-throughput calculations using van der Waals density functional theory, validated against experimental structural data and calculated random phase approximation binding energies, further allowed the identification of 1,825 compounds that are either easily or potentially exfoliable. In particular, the subset of 1,036 easily exfoliable cases provides novel structural prototypes and simple ternary compounds as well as a large portfolio of materials to search from for optimal properties. For a subset of 258 compounds, we explore vibrational, electronic, magnetic and topological properties, identifying 56 ferromagnetic and antiferromagnetic systems, including half-metals and half-semiconductors.The largest available database of potentially exfoliable 2D materials has been obtained via high-throughput calculations using van der Waals density functional theory.

Unveiling mode-selected electron-phonon interactions in metal films by helium atom scattering

The quasi two-dimensional electron gas on a metal film can transmit to the surface even minute mechanical disturbances occurring in the depth, thus allowing the gentlest of all surface probes, helium atoms, to perceive the vibrations of the deepest atoms via the induced surface-charge density oscillations. A density functional perturbation theory (DFPT) and a helium atom scattering study of the phonon dispersion curves in lead films of up to 7 mono-layers on a copper substrate show that: (a) the electron-phonon interaction is responsible for the coupling of He atoms to in-depth phonon modes; and (b) the inelastic HAS intensity from a given phonon mode is proportional to its electron-phonon coupling. The direct determination of mode-selected electron-phonon coupling strengths has great relevance for understanding superconductivity in thin films and two-dimensional systems.

Electron-phonon interaction and thermal boundary resistance at the crystal-amorphous interface of the phase change compound GeTe

Phonon dispersion relations and electron-phonon coupling of hole-doped trigonal GeTe have been computed by density functional perturbation theory. This compound is a prototypical phase change material of interest for applications in phase change non-volatile memories. The calculations allowed us to estimate the electron-phonon contribution to the thermal boundary resistance at the interface between the crystalline and amorphous phases present in the device. The lattice contribution to the thermal boundary resistance has been computed by non-equilibrium molecular dynamics simulations with an interatomic potential based on a neural network scheme. We find that the electron-phonon term contributes to the thermal boundary resistance to an extent which is strongly dependent on the concentration and mobility of the holes. Further, for measured values of the holes concentration and electrical conductivity, the electron-phonon term is larger than the contribution from the lattice. It is also shown that the presence of Ge vacancies, responsible for the p-type degenerate character of the semiconductor, strongly affects the lattice thermal conductivity of the crystal.

Indium selenide: an insight into electronic band structure and surface excitations

We have investigated the electronic response of single crystals of indium selenide by means of angle-resolved photoemission spectroscopy, electron energy loss spectroscopy and density functional theory. The loss spectrum of indium selenide shows the direct free exciton at ~1.3 eV and several other peaks, which do not exhibit dispersion with the momentum. The joint analysis of the experimental band structure and the density of states indicates that spectral features in the loss function are strictly related to single-particle transitions. These excitations cannot be considered as fully coherent plasmons and they are damped even in the optical limit, i.e. for small momenta. The comparison of the calculated symmetry-projected density of states with electron energy loss spectra enables the assignment of the spectral features to transitions between specific electronic states. Furthermore, the effects of ambient gases on the band structure and on the loss function have been probed.

Ordered Peierls distortion prevented at growth onset of GeTe ultra-thin films

Using reflection high-energy electron diffraction (RHEED), the growth onset of molecular beam epitaxy (MBE) deposited germanium telluride (GeTe) film on Si(111)-(√3 × √3)R30°-Sb surfaces is investigated, and a larger than expected in-plane lattice spacing is observed during the deposition of the first two molecular layers. High-resolution transmission electron microscopy (HRTEM) confirms that the growth proceeds via closed layers, and that those are stable after growth. The comparison of the experimental Raman spectra with theoretical calculated ones allows assessing the shift of the phonon modes for a quasi-free-standing ultra-thin GeTe layer with larger in-plane lattice spacing. The manifestation of the latter phenomenon is ascribed to the influence of the interface and the confinement of GeTe within the limited volume of material available at growth onset, either preventing the occurrence of Peierls dimerization or their ordered arrangement to occur normally.

The interaction of organic adsorbate vibrations with substrate lattice waves in methyl-Si(111)-(1 × 1)

A combined helium atom scattering and density functional perturbation theory study has been performed to elucidate the surface phonon dispersion relations for both the CH3-Si(111)-(1 × 1) and CD3-Si(111)-(1 × 1) surfaces. The combination of experimental and theoretical methods has allowed characterization of the interactions between the low energy vibrations of the adsorbate and the lattice waves of the underlying substrate, as well as characterization of the interactions between neighboring methyl groups, across the entire wavevector resolved vibrational energy spectrum of each system. The Rayleigh wave was found to hybridize with the surface rocking libration near the surface Brillouin zone edge at both the M̄-point and K̄-point. The calculations indicated that the range of possible energies for the potential barrier to the methyl rotation about the Si-C axis is sufficient to prevent the free rotation of the methyl groups at a room temperature interface. The density functional perturbation theory calculations revealed several other surface phonons that experienced mode-splitting arising from the mutual interaction of adjacent methyl groups. The theory identified a Lucas pair that exists just below the silicon optical bands. For both the CH3- and CD3-terminated Si(111) surfaces, the deformations of the methyl groups were examined and compared to previous experimental and theoretical work on the nature of the surface vibrations. The calculations indicated a splitting of the asymmetric deformation of the methyl group near the zone edges due to steric interactions of adjacent methyl groups. The observed shifts in vibrational energies of the -CD3 groups were consistent with the expected effect of isotopic substitution in this system.

Vibrational dynamics and band structure of methyl-terminated Ge(111)

A combined synthesis, experiment, and theory approach, using elastic and inelastic helium atom scattering along with ab initio density functional perturbation theory, has been used to investigate the vibrational dynamics and band structure of a recently synthesized organic-functionalized semiconductor interface. Specifically, the thermal properties and lattice dynamics of the underlying Ge(111) semiconductor crystal in the presence of a commensurate (1 × 1) methyl adlayer were defined for atomically flat methylated Ge(111) surfaces. The mean-square atomic displacements were evaluated by analysis of the thermal attenuation of the elastic He diffraction intensities using the Debye-Waller model, revealing an interface with hybrid characteristics. The methyl adlayer vibrational modes are coupled with the Ge(111) substrate, resulting in significantly softer in-plane motion relative to rigid motion in the surface normal. Inelastic helium time-of-flight measurements revealed the excitations of the Rayleigh wave across the surface Brillouin zone, and such measurements were in agreement with the dispersion curves that were produced using density functional perturbation theory. The dispersion relations for H-Ge(111) indicated that a deviation in energy and lineshape for the Rayleigh wave was present along the nearest-neighbor direction. The effects of mass loading, as determined by calculations for CD3-Ge(111), as well as by force constants, were less significant than the hybridization between the Rayleigh wave and methyl adlayer librations. The presence of mutually similar hybridization effects for CH3-Ge(111) and CH3-Si(111) surfaces extends the understanding of the relationship between the vibrational dynamics and the band structure of various semiconductor surfaces that have been functionalized with organic overlayers.

The electron-phonon interaction at deep Bi 2 Te3-semiconductor interfaces from Brillouin light scattering

It is shown that the electron-phonon interaction at a conducting interface between a topological insulator thin film and a semiconductor substrate can be directly probed by means of high-resolution Brillouin light scattering (BLS). The observation of Kohn anomalies in the surface phonon dispersion curves of a 50 nm thick Bi2Te3 film on GaAs, besides demonstrating important electron-phonon coupling effects in the GHz frequency domain, shows that information on deep interface electrons can be obtained by tuning the penetration depth of optically-generated surface phonons so as to selectively probe the interface region, as in a sort of quantum sonar.

Surface lattice dynamics and electron–phonon interaction in cesium ultra-thin films

The phonon dispersion curves of ultrathin films of Cs(110) on Pt(111) measured with inelastic helium atom scattering (HAS) are reported and compared with density-functional perturbation theory (DFPT) calculations. The combined HAS and DFPT analysis also sheds light on the bulk phonon dynamics of bcc-Cs, on which very little is known from neutron scattering due to its large neutron capture cross-section. Moreover the temperature dependence of the elastic HAS Debye-Waller exponent of Cs(110)/Cu(111) ultrathin films allows for an estimation of the electron-phonon coupling strength λ as a function of the film thickness.

Novel 2-D Materials for Tunneling FETs: an Ab-initio Study

An excellent electrostatic control has been early on identified as one of the most critical ingredients to build band- to- band tunneling field-effect transistors (TFETs) with a steep sub-threshold swing (SS) and a high ON-current (ION) [1]. These essential features can be obtained by reducing the thickness of ultra-thin-body structures or the diameter of nanowires. Two-dimensional materials, especially their single-layer (SL) configuration, represent a promising alternative to conventional semiconductors due to their intrinsic sub-1nm thickness. Indeed, a TFET implementing an atomically thin MoS2 channel combined with a Ge layer was recently shown to exhibit a less than 60 mV/dec SS over several orders of magnitude and a decent ION[2]. In this experiment, however, MoS2 had to be grouped with Ge to achieve the desired goal, thus raising the question whether 2-D materials alone can provide a suitable platform for high performance TFETs. Various theoretical studies based on empirical tight-binding models and focusing on SL transition metal dichalcogenides (TMDs) [3] and black phosphorus [4] have come to the conclusion that these compounds, in particular WTe2, could deliver ON-currents larger than