Raman microscopy and infrared optical properties of SiGe Mie resonators formed on SiO2 via Ge condensation and solid state dewetting.

All-dielectric photonics is a rapidly developing field of optics and material science. The main interest at visible and near-infrared frequencies is light management using high-refractive-index Mie-resonant dielectric particles. Most work in this area of research focuses on exploiting Si-based particles. Here, we study monocrystalline Mie-resonant particles made of Ge-rich SiGe alloys with refractive index higher than that of Si. These islands are formed via solid state dewetting of SiGe flat layers by using two different processes: (i) dewetting of monocrystalline SiGe layers (60%-80% Ge content) obtained via Ge condensation of SiGe on silicon on insulator; and (ii) dewetting of a SiGe layer deposited via molecular beam epitaxy on silicon on insulator and ex situ Ge condensation, forming a Ge-rich shell surrounding a SiGe-core. Using high-spatial-resolution Raman microscopy we monitor Ge content x and strain ϵ of flat layers and SiGe-islands. We observe strain relaxation associated with formation of trading dislocations in the SiGe islands compared to the starting SiGe layers, as confirmed by TEM images. For initial high Ge concentration in the flat layers, the corresponding Ge content in the dewetted islands is lower, owing to diffusion of Si atoms from Si or SiO2 into SiGe islands. The Ge content also varies from particle to particle on the same sample. Size and shape of the dewetted particles depend on the fabrication process: thicker initial SiGe layers lead to larger particles. Samples with narrow island size distribution display rather sharp Mie resonances in the 1000-2500 nm spectral range. Larger islands display Mie resonances at longer wavelength. Positions of the resonances are in agreement with the theoretical calculations in the discrete dipole approximation.

Tailoring Strain and Morphology of Core-Shell SiGe Nanowires by Low-Temperature Ge Condensation.

Selective oxidation of the silicon element of silicon germanium (SiGe) alloys during thermal oxidation is a very important and technologically relevant mechanism used to fabricate a variety of microelectronic devices. We develop here a simple integrative approach involving vapor-liquid-solid (VLS) growth followed by selective oxidation steps to the construction of core-shell nanowires and higher-level ordered systems with scalable configurations. We examine the selective oxidation/condensation process under nonequilibrium conditions that gives rise to spontaneous formation of core-shell structures by germanium condensation. We contrast this strategy that uses reaction-diffusion-segregation mechanisms to produce coherently strained structures with highly configurable geometry and abrupt interfaces with growth-based processes which lead to low strained systems with nonuniform composition, three-dimensional morphology, and broad core-shell interface. We specially focus on SiGe core-shell nanowires and demonstrate that they can have up to 70% Ge-rich shell and 2% homogeneous strain with core diameter as small as 14 nm. Key elements of the building process associated with this approach are identified with regard to existing theoretical models. Moreover, starting from results of ab initio calculations, we discuss the electronic structure of these novel nanostructures as well as their wide potential for advanced device applications.

Templated Solid-State Dewetting of Thin Silicon Films.

Thin film dewetting can be efficiently exploited for the implementation of functionalized surfaces over very large scales. Although the formation of sub-micrometer sized crystals via solid-state dewetting represents a viable method for the fabrication of quantum dots and optical meta-surfaces, there are several limitations related to the intrinsic features of dewetting in a crystalline medium. Disordered spatial organization, size, and shape fluctuations are relevant issues not properly addressed so far. This study reports on the deterministic nucleation and precise positioning of Si- and SiGe-based nanocrystals by templated solid-state dewetting of thin silicon films. The dewetting dynamics is guided by pattern size and shape taking full control over number, size, shape, and relative position of the particles (islands dimensions and relative distances are in the hundreds nm range and fluctuate ≈11% for the volumes and ≈5% for the positioning).

Fabrication of core-shell nanostructures via silicon on insulator dewetting and germanium condensation: towards a strain tuning method for SiGe-based heterostructures in a three-dimensional geometry.

We report on a novel method for the implementation of core-shell SiGe-based nanocrystals combining silicon on insulator dewetting in a molecular beam epitaxy reactor with an ex situ Ge condensation process. With an in situ two-step process (annealing and Ge deposition) we produce two families of islands on the same sample: Si-rich, formed during the first step and, all around them, Ge-rich formed after Ge deposition. By increasing the amount of Ge deposited on the annealed samples from 0 to 18 monolayers, the islands' shape in the Si-rich zones can be tuned from elongated and flat to more symmetric and with a larger vertical aspect ratio. At the same time, the spatial extension of the Ge-rich zones is progressively increased as well as the Ge content in the islands. Further processing by ex situ rapid thermal oxidation results in the formation of a core-shell composition profile in both Si and Ge-rich zones with atomically sharp heterointerfaces. The Ge condensation induces a Ge enrichment of the islands' shell of up to 50% while keeping a pure Si core in the Si-rich zones and a ∼25% SiGe alloy in the Ge-rich ones. The large lattice mismatch between core and shell, the absence of dislocations and the islands' monocrystalline nature render this novel class of nanostructures a promising device platform for strain-based band-gap engineering. Finally, this method can be used for the implementation of ultralarge scale meta-surfaces with dielectric Mie resonators for light manipulation at the nanoscale.

Interrupted self-organization of SiGe pyramids.

We investigate the morphological evolution of SiGe quantum dots deposited on Si(100) during long-time annealing. At low strain, the dots' self-organization begins by an instability and interrupts when (105) pyramids form. This evolution and the resulting island density are quantified by molecular-beam epitaxy. A kinetic model accounting for elasticity, wetting, and anisotropy is shown to reproduce well the experimental findings with appropriate wetting parameters. In this nucleationless regime, a mean-field kinetic analysis explains the existence of nearly stationary states by the vanishing of the coarsening driving force. The island size distribution follows in both experiments and theory the scaling law associated with a single characteristic length scale.

Van der Waals Heteroepitaxy of Air-Stable Quasi-Free-Standing Silicene Layers on CVD Epitaxial Graphene/6H-SiC.

Graphene, consisting of an inert, thermally stable material with an atomically flat, dangling-bond-free surface, is by essence an ideal template layer for van der Waals heteroepitaxy of two-dimensional materials such as silicene. However, depending on the synthesis method and growth parameters, graphene (Gr) substrates could exhibit, on a single sample, various surface structures, thicknesses, defects, and step heights. These structures noticeably affect the growth mode of epitaxial layers, e.g., turning the layer-by-layer growth into the Volmer-Weber growth promoted by defect-assisted nucleation. In this work, the growth of silicon on chemical vapor deposited epitaxial Gr (1 ML Gr/1 ML Gr buffer) on a 6H-SiC(0001) substrate is investigated by a combination of atomic force microscopy (AFM), scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and Raman spectroscopy measurements. It is shown that the perfect control of full-scale almost defect-free 1 ML Gr with a single surface structure and the ultraclean conditions for molecular beam epitaxy deposition of silicon represent key prerequisites for ensuring the growth of extended silicene sheets on epitaxial graphene. At low coverages, the deposition of Si produces large silicene sheets (some hundreds of nanometers large) attested by both AFM and SEM observations and the onset of a Raman peak at 560 cm-1, very close to the theoretical value of 570 cm-1 calculated for free-standing silicene. This vibrational mode at 560 cm-1 represents the highest ever experimentally measured value and is representative of quasi-free-standing silicene with almost no interaction with inert nonmetal substrates. From a coverage rate of 1 ML, the silicene sheets disappear at the expense of 3D Si dendritic islands whose density, size, and thickness increase with the deposited thickness. From this coverage, the Raman mode assigned to quasi-free-standing silicene totally vanishes, and the 2D flakes of silicene are no longer observed by AFM. The experimental results are in very good agreement with the results of kinetic Monte Carlo simulations that rationalize the initial flake growth in solid-state dewetting conditions, followed by the growth of ridges surrounding and eventually covering the 2D flakes. A full description of the growth mechanism is given. This study, which covers a wide range of growth parameters, challenges recent results stating the impossibility to grow silicene on a carbon inert surface and is very promising for large-scale silicene growth. It shows that silicene growth can be achieved using perfectly controlled and ultraclean deposition conditions and an almost defect-free Gr substrate.

Photoluminescence efficiency and size distribution of self assembled ge dots on porous TiO2.

For Ge nanodots approximately 20 nm in diameter grown by annealing a thin amorphous Ge layer deposited by molecular beam epitaxy on a mesoporous TiO2 layer on Si(001), photoluminescence (PL) was observed as a wide near-infrared band near 800 meV. Using a tight binding theoretical model, the energy-dependent PL spectrum was transformed into a dependence on dot size. The average dot size determined the peak energy of the PL band and its shape depended on the size distribution, including bandgap enlargement due to quantum confinement. Combining the dot sample PL with an established dependence of emission efficiency on dot diameter, it was possible to derive a dot size distribution and compare it with results obtained independently from atomic force microscopy.

Photocurrent generation in Ge nanocrystal/Si systems.

We report on the generation of photocurrent in the visible and ultraviolet range from planar devices built from the Ge nanocrystals grown on a heavy n-doped Si(001) substrate covered with 5 nm thick thermally grown SiO2. These Ge nanostructures/SiO2/n(+)-Si devices are shown to generate photocurrent with an Incident-Photon-to-electron Conversion Efficiency (IPCE) spectral range depending on the Ge nanocrystals size. The increase of the IPCE value of our devices in the 350-600 nm range correlates well with the absorbance of Ge.

New Strategies for Engineering Tensile Strained Si Layers for Novel n-Type MOSFET.

We report a novel approach for engineering tensely strained Si layers on a relaxed silicon germanium on insulator (SGOI) film using a combination of condensation, annealing, and epitaxy in conditions specifically chosen from elastic simulations. The study shows the remarkable role of the SiO2 buried oxide layer (BOX) on the elastic behavior of the system. We show that tensely strained Si can be engineered by using alternatively rigidity (at low temperature) and viscoelasticity (at high temperature) of the SiO2 substrate. In these conditions, we get a Si strained layer perfectly flat and free of defects on top of relaxed Si1-xGex. We found very specific annealing conditions to relax SGOI while keeping a homogeneous Ge concentration and an excellent thickness uniformity resulting from the viscoelasticity of SiO2 at this temperature, which would allow layer-by-layer matter redistribution. Remarkably, the Si layer epitaxially grown on relaxed SGOI remains fully strained with -0.85% tensile strain. The absence of strain sharing (between Si1-xGex and Si) is explained by the rigidity of the Si1-xGex/BOX interface at low temperature. Elastic simulations of the real system show that, because of the very specific elastic characteristics of SiO2, there are unique experimental conditions that both relax Si1-xGex and keep Si strained. Various epitaxial processes could be revisited in light of these new results. The generic and simple process implemented here meets all the requirements of the microelectronics industry and should be rapidly integrated in the fabrication lines of large multifinger 2.5 V n-type MOSFET on SOI used for RF-switch applications and for many other applications.

Spontaneous shape transition of Mn x Ge1- x islands to long nanowires.

We report experimental evidence for a spontaneous shape transition, from regular islands to elongated nanowires, upon high-temperature annealing of a thin Mn wetting layer evaporated on Ge(111). We demonstrate that 4.5 monolayers is the critical thickness of the Mn layer, governing the shape transition to wires. A small change around this value modulates the geometry of the nanostructures. The Mn-Ge alloy nanowires are single-crystalline structures with homogeneous composition and uniform width along their length. The shape evolution towards nanowires occurs for islands with a mean size of ≃170 nm. The wires, up to ≃1.1 µm long, asymptotically tend to ≃80 nm of width. We found that tuning the annealing process allows one to extend the wire length up to ≃1.5 µm with a minor rise of the lateral size to ≃100 nm. The elongation process of the nanostructures is in agreement with a strain-driven shape transition mechanism proposed in the literature for other heteroepitaxial systems. Our study gives experimental evidence for the spontaneous formation of spatially uniform and compositionally homogeneous Mn-rich GeMn nanowires on Ge(111). The reliable and simple synthesis approach allows one to exploit the room-temperature ferromagnetic properties of the Mn-Ge alloy to design and fabricate novel nanodevices.

Capillary-driven elastic attraction between quantum dots.

We present a novel self-assembly route to align SiGe quantum dots. By a combination of theoretical analyses and experimental investigation, we show that epitaxial SiGe quantum dots can cluster in ordered closely packed assemblies, revealing an attractive phenomenon. We compute nucleation energy barriers, accounting for elastic effects between quantum dots through both elastic energy and strain-dependent surface energy. If the former is mostly repulsive, we show that the decrease in the surface energy close to an existing island reduces the nucleation barrier. It subsequently increases the probability of nucleation close to an existing island, and turns out to be equivalent to an effective attraction between dots. We show by Monte-Carlo simulations that this effect describes well the experimental results, revealing a new mechanism ruling self-organisation of quantum dots. Such a generic process could be observed in various heterogeneous systems and could pave the way for a wide range of applications.

Templated dewetting of single-crystal sub-millimeter-long nanowires and on-chip silicon circuits.

Large-scale, defect-free, micro- and nano-circuits with controlled inter-connections represent the nexus between electronic and photonic components. However, their fabrication over large scales often requires demanding procedures that are hardly scalable. Here we synthesize arrays of parallel ultra-long (up to 0.75 mm), monocrystalline, silicon-based nano-wires and complex, connected circuits exploiting low-resolution etching and annealing of thin silicon films on insulator. Phase field simulations reveal that crystal faceting and stabilization of the wires against breaking is due to surface energy anisotropy. Wires splitting, inter-connections and direction are independently managed by engineering the dewetting fronts and exploiting the spontaneous formation of kinks. Finally, we fabricate field-effect transistors with state-of-the-art trans-conductance and electron mobility. Beyond the first experimental evidence of controlled dewetting of patches featuring a record aspect ratio of [Formula: see text]1/60000 and self-assembled [Formula: see text]mm long nano-wires, our method constitutes a distinct and promising approach for the deterministic implementation of atomically-smooth, mono-crystalline electronic and photonic circuits.

New strategies for producing defect free SiGe strained nanolayers.

Strain engineering is seen as a cost-effective way to improve the properties of electronic devices. However, this technique is limited by the development of the Asarro Tiller Grinfeld growth instability and nucleation of dislocations. Two strain engineering processes have been developed, fabrication of stretchable nanomembranes by deposition of SiGe on a sacrificial compliant substrate and use of lateral stressors to strain SiGe on Silicon On Insulator. Here, we investigate the influence of substrate softness and pre-strain on growth instability and nucleation of dislocations. We show that while a soft pseudo-substrate could significantly enhance the growth rate of the instability in specific conditions, no effet is seen for SiGe heteroepitaxy, because of the normalized thickness of the layers. Such results were obtained for substrates up to 10 times softer than bulk silicon. The theoretical predictions are supported by experimental results obtained first on moderately soft Silicon On Insulator and second on highly soft porous silicon. On the contrary, the use of a tensily pre-strained substrate is far more efficient to inhibit both the development of the instability and the nucleation of misfit dislocations. Such inhibitions are nicely observed during the heteroepitaxy of SiGe on pre-strained porous silicon.

Complex dewetting scenarios of ultrathin silicon films for large-scale nanoarchitectures.

Dewetting is a ubiquitous phenomenon in nature; many different thin films of organic and inorganic substances (such as liquids, polymers, metals, and semiconductors) share this shape instability driven by surface tension and mass transport. Via templated solid-state dewetting, we frame complex nanoarchitectures of monocrystalline silicon on insulator with unprecedented precision and reproducibility over large scales. Phase-field simulations reveal the dominant role of surface diffusion as a driving force for dewetting and provide a predictive tool to further engineer this hybrid top-down/bottom-up self-assembly method. Our results demonstrate that patches of thin monocrystalline films of metals and semiconductors share the same dewetting dynamics. We also prove the potential of our method by fabricating nanotransfer molding of metal oxide xerogels on silicon and glass substrates. This method allows the novel possibility of transferring these Si-based patterns on different materials, which do not usually undergo dewetting, offering great potential also for microfluidic or sensing applications.

van der Waals Heteroepitaxy of Germanene Islands on Graphite.

We fabricated flat, two-dimensional germanium sheets showing a honeycomb lattice that matches that of germanene by depositing submonolayers of Ge on graphite at room temperature and subsequent annealing to 350 °C. Scanning tunneling microscopy shows that the germanene islands have a small buckling with no atomic reconstruction and does not give any hints for alloy formation and hybridization with the substrate. Our density functional theory calculations of the structural properties agree well with our experimental findings and indicate that the germanene sheet interacts only weakly with the substrate underneath. Our band structure calculations confirm that the Dirac cone of free-standing germanene is preserved for layers supported on graphite. The germanene islands show a small but characteristic charge transfer with the graphite substrate which is predicted by our ab initio simulations in excellent agreement with scanning tunneling spectroscopy measurements.

Correction: Fabrication of poly-crystalline Si-based Mie resonators via amorphous Si on SiO2 dewetting.

Correction for 'Fabrication of poly-crystalline Si-based Mie resonators via amorphous Si on SiO2 dewetting' by Meher Naffouti, et al., Nanoscale, 2016, 8, 2844-2849.

Formation of Silicene Nanosheets on Graphite.

The extraordinary properties of graphene have spurred huge interest in the experimental realization of a two-dimensional honeycomb lattice of silicon, namely, silicene. However, its synthesis on supporting substrates remains a challenging issue. Recently, strong doubts against the possibility of synthesizing silicene on metallic substrates have been brought forward because of the non-negligible interaction between silicon and metal atoms. To solve the growth problems, we directly deposited silicon on a chemically inert graphite substrate at room temperature. Based on atomic force microscopy, scanning tunneling microscopy, and ab initio molecular dynamics simulations, we reveal the growth of silicon nanosheets where the substrate-silicon interaction is minimized. Scanning tunneling microscopy measurements clearly display the atomically resolved unit cell and the small buckling of the silicene honeycomb structure. Similar to the carbon atoms in graphene, each of the silicon atoms has three nearest and six second nearest neighbors, thus demonstrating its dominant sp2 configuration. Our scanning tunneling spectroscopy investigations confirm the metallic character of the deposited silicene, in excellent agreement with our band structure calculations that also exhibit the presence of a Dirac cone.

Fabrication of poly-crystalline Si-based Mie resonators via amorphous Si on SiO2 dewetting.

We report the fabrication of Si-based dielectric Mie resonators via a low cost process based on solid-state dewetting of ultra-thin amorphous Si on SiO2. We investigate the dewetting dynamics of a few nanometer sized layers annealed at high temperature to form submicrometric Si-particles. Morphological and structural characterization reveal the polycrystalline nature of the semiconductor matrix as well as rather irregular morphologies of the dewetted islands. Optical dark field imaging and spectroscopy measurements of the single islands reveal pronounced resonant scattering at visible frequencies. The linewidth of the low-order modes can be ∼20 nm in full width at half maximum, leading to a quality factor Q exceeding 25. These values reach the state-of-the-art ones obtained for monocrystalline Mie resonators. The simplicity of the dewetting process and its cost-effectiveness opens the route to exploiting it over large scales for applications in silicon-based photonics.

Si/Ge intermixing during Ge Stranski-Krastanov growth.

The Stranski-Krastanov growth of Ge islands on Si(001) has been widely studied. The morphology changes of Ge islands during growth, from nucleation to hut/island formation and growth, followed by hut-to-dome island transformation and dislocation nucleation of domes, have been well described, even at the atomic scale, using techniques such as scanning tunneling microscopy and transmission electron microscopy. Although it is known that these islands do not consist of pure Ge (due to Si/Ge intermixing), the composition of the Ge islands is not precisely known. In the present work, atom probe tomography was used to study the composition of buried dome islands at the atomic scale, in the three-dimensional space. The core of the island was shown to contain about 55 atom % Ge, while the Ge composition surrounding this core decreases rapidly in all directions in the islands to reach a Ge concentration of about 15 atom %. The Ge distribution in the islands follows a cylindrical symmetry and Ge segregation is observed only in the {113} facets of the islands. The Ge composition of the wetting layer is not homogeneous, varying from 5 to 30 atom %.

Wafer scale formation of monocrystalline silicon-based Mie resonators via silicon-on-insulator dewetting.

Subwavelength-sized dielectric Mie resonators have recently emerged as a promising photonic platform, as they combine the advantages of dielectric microstructures and metallic nanoparticles supporting surface plasmon polaritons. Here, we report the capabilities of a dewetting-based process, independent of the sample size, to fabricate Si-based resonators over large scales starting from commercial silicon-on-insulator (SOI) substrates. Spontaneous dewetting is shown to allow the production of monocrystalline Mie-resonators that feature two resonant modes in the visible spectrum, as observed in confocal scattering spectroscopy. Homogeneous scattering responses and improved spatial ordering of the Si-based resonators are observed when dewetting is assisted by electron beam lithography. Finally, exploiting different thermal agglomeration regimes, we highlight the versatility of this technique, which, when assisted by focused ion beam nanopatterning, produces monocrystalline nanocrystals with ad hoc size, position, and organization in complex multimers.