arXiv subjects

Emilio Scalise

Publications and source records attributed to Emilio Scalise.

13 recordsLinked to original sources

arXiv2026

Growth and characterization of planar hexagonal Ge on CdS

Hexagonal group-IV semiconductors have attracted increasing interest owing to their unconventional electronic and optical properties compared to the cubic diamond phase. However, the stabilization of these metastable allotropes in planar heterostructures remains a major challenge. In this work, we demonstrate the epitaxial growth of planar hexagonal germanium on non-basal $m$-plane CdS substrates by low-energy plasma-enhanced chemical vapor deposition. The role of growth temperature in the formation and stabilization of the hexagonal phase is investigated. X-ray diffraction, scanning transmission electron microscopy, and polarization-resolved Raman spectroscopy reveal the formation of epitaxial hexagonal germanium with the expected crystal symmetry. In particular, the Raman response exhibits the characteristic polarization selection rules of the E$_\text{2g}$ phonon mode of hexagonal Ge. Conversely, photoluminescence spectroscopy does not reveal any Ge-related emission feature. Combined transmission electron microscopy observations and atomistic modeling show that strain relaxation is governed by a limited set of dislocation mechanisms, which efficiently relieve most of the mismatch strain within a few nanometers from the interface and can involve localized cubic stacking insertions. At greater distances from the interface, the progressive loss of hexagonal order is increasingly dominated by stacking-fault disorder, particularly I3-type defects. These results establish CdS as a promising template for the planar stabilization of hexagonal Ge and provide insight into the defect mechanisms governing strain relaxation in metastable group-IV heterostructures.

cond-mat.mtrl-sci↗

arXiv2026

Resolving the Metastable Si-XIII Structure through Convergent Theory and Experiment

Silicon is the undisputed cornerstone of modern technology, with applications ranging from micro- and opto-electronics to quantum technologies. Recently, the exploration of its allotropes has emerged as a pivotal frontier for engineering materials with tailored optical and electronic functionalities. High-pressure experiments have revealed several metastable silicon phases, among which is Si-XIII. First observed more than 20 years ago, this phase has remained structurally unidentified, representing a significant gap in our understanding of elemental silicon allotropy. In this work, a convergent methodology is employed combining advanced theoretical modeling with experimental characterization to finally resolve the long-standing structural assignment of Si-XIII. Guided by careful experimental observations, a structural model validated through first-principles optimization and systematically tested against multiple experimental signatures is constructed. All the fingerprints of this phase are rationalized by our proposed crystal structure: interplanar spacings, Raman frequencies, thermodynamic stability, and kinetic pathways. These findings provide a crucial missing piece in the high-pressure phase diagram of silicon and demonstrate the power of integrating computational predictions with experimental validation to resolve complex structural problems in materials science.

cond-mat.mtrl-sci↗

arXiv2026

Interface stability of beta-Ga2O3 (100) on oxidized Si- and C-terminated 3C-SiC (001) substrates: a first-principles investigation

We provide a first-principles modeling of the beta-Ga2O3/3C-SiC interface that takes into account the reconstructions occurring at the 3C-SiC (001) surface by oxidation, aiming to mimic the actual deposition process under the best structural and thermodynamic conditions. Using density functional theory calculations, we systematically investigate the interface configurations between beta-Ga2O3 (100) and both Si- and C-terminated 3C-SiC (001) substrates, considering realistic oxidation states that form at the SiC surface prior to epitaxial growth. Our analysis evaluates different stacking sequences and atomic-scale bonding arrangements, computing adhesion energies for various interface geometries to determine their relative thermodynamic stability. This work addresses the critical need for understanding beta-Ga2O3 integration on substrates with superior thermal conductivity, providing a theoretical framework for optimizing heteroepitaxial growth conditions in ultra-wide-bandgap power electronics applications.

cond-mat.mtrl-sci↗

arXiv2026

Electronic States, Spin-Orbit Coupling and Magnetism in Germanium 60{\deg} Dislocations

Defects in semiconductors have recently attracted renewed interest owing to their potential in novel quantum applications. Here we investigate the electronic and magnetic properties induced by 60{\deg} dislocations in Ge. Using large-scale DFT calculations, we determine the band structure for both the shuffle and glide sets in their lowest-energy configurations. We also perform charged-defect calculations to aid in the interpretation of complex photoluminescence spectra observed in epitaxial Ge layers. The band structure for the shuffle set reveals defect-induced dispersive bands localized within the band gap near the {\Gamma} point, whereas for the glide set, we observe strong overlap with the conduction band. Defect-induced band splitting evident away from {\Gamma} reveals Rashba-Dresselhaus spin-orbit coupling, an effect previously reported only for screw dislocations. Remarkably, we find evidence that specific dislocation arrangements can stabilize antiferromagnetic ordering with sizable local magnetic moments and considerable exchange splitting between opposite spin states. These results uncover rich physics in Ge dislocations through the combination of spin-orbit coupling and magnetic ordering, potentially enabling novel defect-based functionalities in Ge devices.

cond-mat.mtrl-sci↗

arXiv2025

Interaction of dopants with the I$_3$-type basal stacking fault in hexagonal-diamond Si

Recently synthesized hexagonal-diamond silicon, germanium, and silicon-germanium nanowires exhibit remarkable optical and electronic properties when compared to cubic-diamond polytypes. Because of the metastability of the hexagonal-diamond phase, I$_3$-type basal stacking faults are frequently observed in these materials. Understanding and modulating the interaction between these extended defects and dopants are essential for advancing the design and performance of these novel semiconductors. In the present study, we employ density functional theory calculations to investigate the interaction of extrinsic dopants (group III, IV, and V elements) with the I$_3$-type basal stacking fault in hexagonal-diamond silicon. Contrary to the behavior observed in cubic-diamond silicon with intrinsic stacking faults, we demonstrate that neutral and negatively charged $p$-type impurities exhibit a marked tendency to occupy lattice sites far from the I$_3$-type basal stacking fault. The interaction of acceptors with the planar defect reduces their energetic stability. However, this effect is much less pronounced for neutral or positively charged $n$-type dopants and isovalent impurities. The thermodynamic energy barrier to segregation for these dopants is small and may even become negative, indicating a tendency to segregate into the fault. Through a detailed analysis of structural modifications, ionization effects, and impurity-level charge density distribution, we show that the origin of this behavior can be attributed to variations in the impurity's steric effects and its wave function character. Finally, all these results are validated by considering the extreme case of an abrupt hexagonal/cubic silicon interface, where acceptor segregation from the cubic to the hexagonal region is demonstrated, confirming the behavior observed for $p$-type dopants near the I$_3$-type defect.

cond-mat.mtrl-sci↗

arXiv2024

Interface energies of Ga2O3 phases with the sapphire substrate and the phase-locked epitaxy of metastable structures explained

Despite the extensive work carried out on the epitaxial growth of Ga2O3, a fundamental understanding of the nucleation of its different metastable phases is still lacking. Here we address the role of interface energies by Density Functional Theory calculations of alpha, beta and kappa Ga2O3 on (0001) Al2O3 substrates, and different Ga2O3 interlayers. In conjunction to surface energies and misfit strain contribution, we demonstrate that alpha Ga2O3 is the preferred phase in 2D islands, when the low growth temperatures and the high growth rates hinder 3D island nucleation. This quantitatively explains the phase-locking in Mist-CVD experiments

cond-mat.mtrl-sci↗

arXiv2024

Formation of Micrometer-Sized Textured Hexagonal Silicon Crystals via Nanoindentation

We present a comprehensive study on the formation of micrometer-sized, textured hexagonal diamond silicon (hd-Si) crystals via nanoindentation followed by annealing. Utilizing advanced characterization techniques such as polarized Raman spectroscopy, high-resolution transmission electron microscopy, and electron energy-loss spectroscopy, we demonstrate the successful transformation of silicon into high-quality hd-Si. The experimental results are further supported by first-principles calculations and molecular dynamics simulations. Notably, the hd-Si phase consists of nanometer-sized grains with slight misorientations, organized into large micrometer-scale textured domains. These findings underscore the potential of nanoindentation as a precise and versatile tool for inducing pressure-driven phase transformations, particularly for the stabilization of hexagonal silicon. The textured nature of hd-Si also presents a unique opportunity to tailor its optical properties, opening new avenues for its application in semiconductor and optoelectronic devices.

cond-mat.mtrl-sci↗

arXiv2024

Unraveling the Atomic-Scale Pathways Driving Pressure-Induced Phase Transitions in Silicon

Silicon exhibits several metastable allotropes which recently attracted attention in the quest for materials with superior (e.g. optical) properties, compatible with Si technology. In this work we shed light on the atomic-scale mechanisms leading to phase transformations in Si under pressure. To do so, we synergically exploit different state-of-the-art approaches. In particular, we use the advanced GAP interatomic potential both in NPT molecular dynamics simulations and in solid-state nudged elastic band calculations, validating our predictions with ab initio DFT calculations. We provide a link between evidence reported in experimental nanoindentation literature and simulation results. Particular attention is dedicated to the investigation of atomistic transition paths allowing for the transformation between BC8/R8 phases to the hd one under pure annealing. In this case we show a direct simulation of the local nucleation of the hexagonal phase in a BC8/R8 matrix and its corresponding atomic-scale mechanism extracted by the use of SS-NEB. We extend our study investigating the effect of pressure on the nucleation barrier, providing an argument for explaining the heterogeneous nucleation of the hd phase observed in experiments reported in the literature.

cond-mat.mtrl-sci↗

arXiv2024

Polytypic Quantum Wells in Si and Ge: Impact of 2D Hexagonal Inclusions on Electronic Band Structure

Crystal defects, traditionally viewed as detrimental, are now being explored for quantum technology applications. This study focuses on stacking faults in silicon and germanium, forming hexagonal inclusions within the cubic crystal and creating quantum wells that modify electronic properties. By modeling defective structures with varying hexagonal layer counts, we calculated formation energies and electronic band structures. Our results show that hexagonal inclusions in Si and Ge exhibit a direct band gap, changing with inclusion thickness, effectively functioning as quantum wells. We find that Ge inclusions have a direct band gap and form Type-I quantum wells. This research highlights the potential of manipulating extended defects to engineer the optoelectronic properties of Si and Ge, offering new pathways for advanced electronic and photonic device applications.

cond-mat.mtrl-sci↗

arXiv2023

Indirect exciton-phonon dynamics in MoS2 revealed by ultrafast electron diffraction

Transition metal dichalcogenides layered nano-crystals are emerging as promising candidates for next-generation optoelectronic and quantum devices. In such systems, the interaction between excitonic states and atomic vibrations is crucial for many fundamental properties, such as carrier mobilities, quantum coherence loss, and heat dissipation. In particular, to fully exploit their valley-selective excitations, one has to understand the many-body exciton physics of zone-edge states. So far, theoretical and experimental studies have mainly focused on the exciton-phonon dynamics in high-energy direct excitons involving zone-center phonons. Here, we use ultrafast electron diffraction and ab initio calculations to investigate the many-body structural dynamics following nearly-resonant excitation of low-energy indirect excitons in MoS2. By exploiting the large momentum carried by scattered electrons, we identify the excitation of in-plane K- and Q-phonon modes with E^' symmetry as key for the stabilization of indirect excitons generated via near-infrared light at 1.55 eV, and we shed light on the role of phonon anharmonicity and the ensuing structural evolution of the MoS2 crystal lattice. Our results highlight the strong selectivity of phononic excitations directly associated with the specific indirect-exciton nature of the wavelength-dependent electronic transitions triggered in the system.

cond-mat.mes-hall↗

arXiv2020

Origin and nature of killer defects in 3C-SiC for power electronic applications by a multiscale atomistic approach

3C-SiC epitaxially grown on Si displays a large wealth of extended defects. In particular, single, double and triple stacking faults (SFs) are observed in several experiments to coexist. Overabundance of defects has so far limited the exploitation of 3C-SiC/Si for power electronics, in spite of its several ideal properties (mainly in terms of wide gap, high breakdown fields and thermal properties) and the possibility of a direct integration in the Si technology. Here we use a multiscale approach, based on both classical molecular dynamics (MD) simulations and first-principle calculations, to investigate in-depth the origin, nature and properties of most common 3C-SiC/Si(001) extended defects. Our MD simulations reveal a natural path for the formation of partial dislocation complexes terminating both double and triple SF's. MD results are used as input for superior DFT calculations, allowing us to better determine the core structure and to investigate electronic properties. It turns out that the partial dislocation complexes terminating double and triple SFs are responsible for the introduction of electronic states significantly filling the gap. On the other hand, individual partial dislocations terminating single SFs only induce states very close to the gap edge. We conclude that partial dislocation complexes, in particular the most abundant triple ones, are killer defects in terms of favoring leakage currents. Suggestions coming from theory/simulations for devising a strategy to lower their occurrence are discussed.

cond-mat.mtrl-sci↗

arXiv2020

Kinetic Control of Morphology and Composition in Ge/GeSn Core/Shell Nanowires

The growth of Sn-rich group-IV semiconductors at the nanoscale provides new paths for understanding the fundamental properties of metastable GeSn alloys. Here, we demonstrate the effect of the growth conditions on the morphology and composition of Ge/GeSn core/shell nanowires by correlating the experimental observations with a theoretical interpretation based on a multi-scale approach. We show that the cross-sectional morphology of Ge/GeSn core/shell nanowires changes from hexagonal to dodecagonal upon increasing the supply of the Sn precursor. This transformation strongly influences the Sn distribution as a higher Sn content is measured under the {112} growth front. Ab-initio DFT calculations provide an atomic-scale explanation by showing that Sn incorporation is favored at the {112} surfaces, where the Ge bonds are tensile-strained. A phase-field continuum model was developed to reproduce the morphological transformation and the Sn distribution within the wire, shedding light on the complex growth mechanism and unveiling the relation between segregation and faceting. The tunability of the photoluminescence emission with the change in composition and morphology of the GeSn shell highlights the potential of the core/shell nanowire system for opto-electronic devices operating at mid-infrared wavelengths.

cond-mat.mtrl-sci↗

arXiv2019

Temperature-dependent stability of polytypes and stacking faults in SiC: reconciling theory and experiments

The relative stability of SiC polytypes, changing with temperature, has been considered a paradox for about thirty years, due to discrepancies between theory and experiments. Based on ab-initio calculations including van der Waals corrections, a temperature-dependent polytypic diagram consistent with the experimental observations is obtained. Results are easily interpreted based on the influence of the hexagonality on both cohesive energy and entropy. Temperature-dependent stability of stacking faults is also analyzed and found to be in agreement with experimental evidences. Our results suggest that lower temperatures during SiC crystal deposition are advantageous in order to reduce ubiquitous stacking faults in SiC-based power devices.

cond-mat.mtrl-sci↗