Cesar E. P. Villegas

Anomalous Temperature Dependence of the Band Gap in Black Phosphorus

Black phosphorus (BP) has gained renewed attention due to its singular anisotropic electronic and optical properties that might be exploited for a wide range of technological applications. In this respect, the thermal properties are particularly important both to predict its room temperature operation and to determine its thermoelectric potential. From this point of view, one of the most spectacular and poorly understood phenomena is indeed the BP temperature-induced band gap opening; when temperature is increased, the fundamental band gap increases instead of decreases. This anomalous thermal dependence has also been observed recently in its monolayer counterpart. In this work, based on ab initio calculations, we present an explanation for this long known and yet not fully explained effect. We show that it arises from a combination of harmonic and lattice thermal expansion contributions, which are in fact highly interwined. We clearly narrow down the mechanisms that cause this gap opening by identifying the peculiar atomic vibrations that drive the anomaly. The final picture we give explains both the BP anomalous band gap opening and the frequency increase with increasing volume (tension effect).

Optical spectrum of bottom-up graphene nanoribbons: towards efficient atom-thick excitonic solar cells

Recently, atomically well-defined cove-shaped graphene nanoribbons have been obtained using bottom-up synthesis. These nanoribbons have an optical gap in the visible range of the spectrum which make them candidates for donor materials in photovoltaic devices. From the atomistic point of view, their electronic and optical properties are not clearly understood. Therefore, in this work we carry out ab-initio density functional theory calculations combine with many-body perturbation formalism to study their electronic and optical properties. Through the comparison with experimental measurements, we show that an accurate description of the nanoribbons optical properties requires the inclusion of electron-hole correlation effects. The energy, binding energy and the corresponding excitonic transitions involved are analyzed. We found that in contrast to zigzag graphene nanoribbons, the excitonic peaks in the absorption spectrum are a consequence of a group of transitions involving the first and second conduction and valence bands. Finally, we estimate some relevant optical properties that strengthen the potential of these nanoribbons for acting as a donor materials in photovoltaic.

Two-dimensional exciton properties in monolayer semiconducting phosphorus allotropes

Excitons play a key role in technological applications since they have a strong influence on determining the efficiency of photovoltaic devices. Recently, it has been shown that the allotropes of phosphorus possess an optical band gap that can be tuned over a wide range of values including the near-infrared and visible spectra, which would make them promising candidates for optoelectronic applications. In this work we carry out ab initio many-body perturbation theory calculations to study the excitonic effects on the optical properties of two-dimensional phosphorus allotropes: the case of blue and black monolayers. We elucidate the most relevant optical transitions, exciton binding energy spectrum as well as real-space exciton distribution, particularly focusing on the absorption spectrum dependence on the incident light polarization. In addition, based on our results, we use a set of effective hydrogenic models, in which the electron-hole Coulomb interaction is included to estimate exciton binding energies and radii. Our results show an excellent agreement between the many-body methodology and the effective models.

Electron-phonon scattering effects on electronic and optical properties of orthorhombic GeS

Group-VI monochalcogenides are attracting a great deal of attention due to their peculiar anisotropic properties. Very recently, it has been suggested that GeS could act as a promissory absorbing material with high input-output ratios, which are relevant features for designing prospective optoelectronic devices. In this work, we use the ab initio many-body perturbation theory to study the role of electron-phonon coupling on orthorhombic GeS. We identify the vibrational modes that efficiently couple with the electronic states responsible for giving rise to the first and second excitonic state. We also study finite-temperature optical absorption, and we show that even at

Ultrafast charge transfer dynamics pathways in two-dimensional MoS2–graphene heterostructures: a core-hole clock approach

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Anomalous lattice vibrations of orthorhombic black phosphorus

, the role of the electron-phonon interaction is crucial to properly describe the position and width of the main experimental excitation peaks. Our results suggest that the electron-phonon coupling is essential to properly describe the optical properties of the monochalcogenides family.