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The chemical vapor deposition of silicon on a patterned silicon substrate leads to the formation of 3D microcrystals, which, due to their inclined top facets and high aspect ratio, produce a light-trapping effect enhancing the optical absorption in the near-infrared (NIR). In this work, it is demonstrated that Si microcrystals can form the building blocks of a new class of NIR sensitive photodetectors operating in a linear or avalanche regime. Microcrystal-based devices are designed by coupling a 2D kinetic-growth model with a Poisson drift-diffusion solver and fabricated by combining electron beam lithography and low-energy plasma-enhanced chemical vapor deposition (LEPECVD). The optoelectronic properties of microcrystal-based p–i–n photodiodes are investigated both theoretically and experimentally by means of finite-difference time-domain (FDTD) simulations and responsivity measurements. At 1000 nm wavelength, the responsivity of microcrystal-based devices is six times higher than that of an equivalent mesa diode. Moreover, the photocurrent gains of Si microcrystals operating as an avalanche photodiode (APD), at the same wavelength, reaches 2 × 104 demonstrating the potentialities of substrate patterning, combined with epitaxial growth, for amplified photodetection applications.

Closing the gap between experiments and simulations in the investigation of high-pressure silicon phase transitions calls for advanced, new-generation modeling approaches. By exploiting massive parallelization, we here provide molecular dynamics (MD) simulations of Si nanoindentation based on the Gaussian Approximation Potential (GAP). Results are analyzed by exploiting a customized Neural Network Phase Recognition (NN-PR) approach, helping to shed light on the phase transitions occurring during the simulations. Our results show that GAP provides a realistic description of silicon phase transitions. With the support of NN-PR method, the formation mechanism and stability of high-pressure phases are comprehensively studied. Additionally, we also show how simulations based on the less demanding and widely-used Tersoff potential are still useful to investigate the role played by the indenter tip modeling. However, high-pressure phases obtained with GAP are more consistent with observations made in nanoindentation experiments, removing a spurious phase that is shown by Tersoff simulations. This behavior is explained on the base of relative phase stability with comparison with Density Functional Theory (DFT) calculations. This work provides insight into the application of state-of-the-art Machine Learning (ML) methods on nanoindentation simulations, enabling further understanding of the phase transition mechanisms in silicon.

Predicted topological crystalline insulators such as Pb1−xSnxTe are an interesting candidate for applications in quantum technology, as they can host spin-polarized surface states. Moreover, in the nanowire geometry, a quasi-1D system can be realized with potential applications exploiting Majorana fermions. Herein, the selective area growth of Pb1−xSnxTe islands and nanowires over the full range of x is demonstrated, and their in-depth growth dynamics and faceting are analyzed. By transmission electron microscopy, the single-crystalline and defect-free nature of the grown material and the homogeneous, controllable Pb/Sn ratio in the nanowires is confirmed. With support of phase-field growth simulations, it is shown that the crystal faceting mainly follows the driving force of surface energy minimization, favoring the lowest energy {200} surfaces. A kinetic enhancement of adatom incorporation on {110} facets is recognized to limit their extension with respect to {200} and {111} facets. After inspecting all possible in-plane orientations, we identify the <110> directions as the optimal candidate for the growth of high-quality and perfectly straight Pb1−xSnxTe nanowires, enabling the design of complex networks due to their threefold symmetry. This work opens the way to systematic transport investigation of the carrier density in Pb1−xSnxTe nanowires and can facilitate further optimization of the Pb1−xSnxTe system.

In this paper, we address the unique nature of fully textured, high surface-to-volume 3C-SiC films, as produced by intrinsic growth anisotropy, in turn generated by the high velocity of the stacking fault growth front in two-dimensional (111) platelets. Structural interpretation of high resolution scanning electron microscopy and transmission electron microscopy data is carried out for samples grown in a hot-wall low-pressure chemical vapour deposition reactor with trichlorosilane and ethylene precursors, under suitable deposition conditions. By correlating the morphology and the X-ray diffraction analysis we also point out that twinning along (111) planes is very frequent in such materials, which changes the free-platelet configuration.

In this review paper, several new approaches about the 3C‐SiC growth are been presented. In fact, despite the long research activity on 3C‐SiC, no devices with good electrical characteristics have been obtained due to the high defect density and high level of stress. To overcome these problems, two different approaches have been used in the last years. From one side, several compliance substrates have been used to try to reduce both the defects and stress, while from another side, the first bulk growth has been performed to try to improve the quality of this material with respect to the heteroepitaxial one. From all these studies, a new understanding of the material defects has been obtained, as well as regarding all the interactions between defects and several growth parameters. This new knowledge will be the basis to solve the main issue of the 3C‐SiC growth and reach the goal to obtain a material with low defects and low stress that would allow for realizing devices with extremely interesting characteristics.

Formation of Ge-rich prismatic inclusions in the hexagonal SiGe shell of GaP-Si-SiGe nanowires is reported and discussed in relation to a growth model that explains their origin. An accurate TEM/EDX analysis shows that such prisms develop right on top of any {1120} facet present on the inner GaP-Si surface, with the base matching the whole facet extension, as large as tens of nanometers, and extending within the SiGe shell up to a thickness of comparable size. An enrichment in Ge by around 5% is recognized within such regions. A phase-field growth model, tackling both the morphological and compositional evolution of the SiGe shell during growth, is exploited to assess the mechanism behind the prism formation. A kinetic segregation process, stemming from the difference in surface mobility between Ge (faster) and Si (slower), is shown to take place, in combination with the evolution of the SiGe shell morphology. Actually, the latter moves from the one templated by the underlying GaP-Si core, including both {1010} and {1120} facets, to the more energetically convenient hexagon, bounded by {1010} facets only. Simulations are shown to accurately reproduce the experimental observations for both regular and asymmetric nanowires. It is then discussed how a careful control of the GaP core faceting, as well as a proper modulation of the shell growth rate, allows for direct control of the appearance and size of the Ge-rich prisms. This tunability paves the way for a possible exploitation of these lower-gap regions for advanced designs of band-gap-engineering.

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Recently synthesized hexagonal group IV materials are a promising platform to realize efficient light emission that is closely integrated with electronics. A high crystal quality is essential to assess the intrinsic electronic and optical properties of these materials unaffected by structural defects. Here, we identify a previously unknown partial planar defect in materials with a type I3 basal stacking fault and investigate its structural and electronic properties. Electron microscopy and atomistic modeling are used to reconstruct and visualize this stacking fault and its terminating dislocations in the crystal. From band structure calculations coupled to photoluminescence measurements, we conclude that the I3 defect does not create states within the hex-Ge and hex-Si band gap. Therefore, the defect is not detrimental to the optoelectronic properties of the hex-SiGe materials family. Finally, highlighting the properties of this defect can be of great interest to the community of hex-III-Ns, where this defect is also present.

The growth of multi-layer germanium-tin (GeSn) quantum wells offers an intriguing pathway towards the integration of lasers in a CMOS platform. An important step in growing high quality quantum well interfaces is the formation of an initial wetting layer. However, key atomic-scale details of this process have not previously been discussed. We use scanning tunneling microscopy combined with density functional theory to study the deposition of Sn on Ge(1 0 0) at room temperature over a coverage range of 0.01 to 1.24 monolayers. We demonstrate the formation of a sub-2% Ge content GeSn wetting layer from three atomic-scale characteristic ad-dimer structural components, and show that small quantities of Sn incorporate into the Ge surface forming two atomic configurations. The ratio of the ad-dimer structures changes with increasing Sn coverage, indicating a change in growth kinetics. At sub-monolayer coverage, the least densely packing ad-dimer structure is most abundant. As the layer closes, forming a two-dimensional wetting layer, the more densely packing ad-dimer structure become dominant. These results demonstrate the capability to form an atomically smooth wetting layer at room temperature, and provide critical atomic-scale insights for the optimization of growth processes of GeSn multi-quantum-wells to meet the quality requirements of optical GeSn-based devices.

The metastable hexagonal-diamond phase of Si and Ge (and of SiGe alloys) displays superior optical properties with respect to the cubic-diamond one. Based on first-principle calculations we show that the surface energy of the typical facets exposed in Si and Ge nanowires is lower in the hexagonal-diamond phase than in the cubic one. By exploiting a synergic approach based also on a recent state-of-the-art interatomic potential and on a simple geometrical model, we investigate the relative stability of nanowires in the two phases up to few tens of nm in radius, highlighting the surface-related driving force and discussing its relevance in recent experiments. We also explore the stability of Si and Ge core-shell nanowires with hexagonal cores (made of GaP for Si nanowires, of GaAs for Ge nanowires). In this case, the stability of the hexagonal shell over the cubic one is also favored by the energy cost associated with the interface linking the two phases. Interestingly, our calculations indicate a critical radius of the hexagonal shell much lower than the one reported in recent experiments, indicating the presence of a large kinetic barrier allowing for the enlargement of the wire in a metastable phase.

The presence of extended bi-dimensional defects is one of the key issues that hinder the use of wide band-gap materials hetero-epitaxially grown on silicon. In this work, we investigate, by STEM measurements and molecular dynamic simulations, the structure of two of the most important extended defect affecting the properties of cubic silicon carbide, 3C-SiC, hetero-epitaxially grown on (001) silicon substrates: (1) stacking faults (SFs) with their bounding threading dislocation arms, even along with unusual directions, and (2) inverted domain boundaries (IDBs). We found that these two defects are strictly correlated: IDBs lying in {111} planes are intrinsically coupled to one or more SFs. Moreover, we observed that threading partial dislocations (PDs), limiting the SFs, appear to have non-conventional line directions, such as [112], [123], and [134]. Molecular dynamics simulations show that [110] and [112] directions allow for stable dislocation structures, while in the unusual [123] and [134] directions, the PDs are composed of zig-zag dislocation lines in the [112] and [110] directions.

3C-SiC epitaxially grown on Si displays a large wealth of extended defects. In particular, single, double and triple stacking faults (SFs) are observed to coexist in several experiments. 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 the wide gap, high breakdown fields and thermal properties) and the possibility of direct integration in the Si technology. Here we use a multiscale approach, based on both classical molecular dynamics (MD) simulations and first-principles calculations, for the in-depth investigation of 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 SFs. The MD results are used as an 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 band 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.

We present an experimental and theoretical analysis of the formation of nanovoids within Si microcrystals epitaxially grown on Si patterned substrates. The growth conditions leading to the nucleation of nanovoids have been highlighted, and the roles played by the deposition rate, substrate temperature, and substrate pattern geometry are identified. By combining various scanning and transmission electron microscopy techniques, it has been possible to link the appearance pits of a few hundred nanometer width at the microcrystal surface with the formation of nanovoids within the crystal volume. A phase-field model, including surface diffusion and the flux of incoming material with shadowing effects, reproduces the qualitative features of the nanovoid formation thereby opening new perspectives for the bottom-up fabrication of 3D semiconductors microstructures.

The growth of Sn-rich group-IV semiconductors at the nanoscale can enrich the understanding of 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 multiscale 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 optoelectronic devices operating at mid-infrared wavelengths.

Compositional segregation is commonly observed during the growth of III-V alloys in core-shell nanowires. Nanometer-thin stripes, enriched in one of the alloy components, are observed along the six <1 1 2> directions perpendicular to the [1 1 1]-wire axis, departing from the core to the outer shell edges in between the {1 1 0} faceted sidewalls. While it has been well established that the phenomenon occurs because of the different mobility of the alloy components, the actual mechanisms by which it happens are yet unclear. A phase-field model, coupling deposition and surface diffusion dynamics, is here developed to inspect the simultaneous evolution of the shell morphology and composition during growth. Both surface energy anisotropy and orientation-dependent growth rates are taken into account to identify their different role. Simulations reveal that the observed segregation is mainly triggered by the enhanced growth rate at the facet edges, while surface anisotropy keeps the stripes thin. Polarity effects are also included to differentiate the behavior between <1 1 2>A and <1 1 2>B orientations, so to reproduce the experimental observation of a 3-fold symmetry.

Strain engineering in Sn-rich group IV semiconductors is a key enabling factor to exploit the direct bandgap at mid-infrared wavelengths. Here, we investigate the effect of strain on the growth of GeSn alloys in a Ge/GeSn core/shell nanowire geometry by controlling the Ge core diameter and correlating the results with theoretical strain calculations. Incorporation of the Sn content in the 10-20 at. % range is achieved with Ge core diameters ranging from 50 nm to 100 nm. While the smaller cores lead to the formation of a regular and homogeneous GeSn shell, larger cores lead to the formation of multifaceted sidewalls and broadened segregation domains, inducing the nucleation of defects. This behavior is rationalized in terms of the different residual strain, as obtained by realistic finite element method simulations. The extended analysis of the strain relaxation as a function of core and shell sizes, in comparison with the conventional planar geometry, provides a deeper understanding of the role of strain in the epitaxy of metastable GeSn semiconductors.

We demonstrate the growth of low density anti-phase boundaries, crack-free GaAs epilayers, by Molecular Beam Epitaxy on silicon (001) substrates. The method relies on the deposition of thick GaAs on a suspended Ge buffer realized on top of deeply patterned Si substrates by means of a three-temperature procedure for the growth. This approach allows to suppress, at the same time, both threading dislocations and thermal strain in the epilayer and to remove anti-phase boundaries even in absence of substrate tilt. Photoluminescence measurements show the good uniformity and the high optical quality of AlGaAs/GaAs quantum well structures realized on top of such GaAs layer.