Electric Field-Induced Nano-Assembly Formation: First Evidence of Silicon Superclusters with a Giant Permanent Dipole Moment.

The outstanding properties of silicon nanoparticles have been extensively investigated during the last few decades. Experimental evidence and applications of their theoretically predicted permanent electric dipole moment, however, have only been reported for silicon nanoclusters (SiNCs) for a size of about one to two nanometers. Here, we have explored the question of whether suitable plasma conditions could lead to much larger silicon clusters with significantly stronger permanent electric dipole moments. A pulsed plasma approach was used for SiNC production and surface deposition. The absorption spectra of the deposited SiNCs were recorded using enhanced darkfield hyperspectral microscopy and compared to time-dependent DFT calculations. Atomic force microscopy and transmission electron microscopy observations completed our study, showing that one-to-two-nanometer SiNCs can, indeed, be used to assemble much larger "superclusters" with a size of tens of nanometers. These superclusters possess extremely high permanent electric dipole moments that can be exploited to orient and guide these clusters with external electric fields, opening the path to the controlled architecture of silicon nanostructures.

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.

Deposition of hydrogenated silicon clusters for efficient epitaxial growth.

Epitaxial silicon thin films grown from the deposition of plasma-born hydrogenated silicon nanoparticles using plasma-enhanced chemical vapor deposition have widely been investigated due to their potential applications in photovoltaic and nanoelectronic device technologies. However, the optimal experimental conditions and the underlying growth mechanisms leading to the high-speed epitaxial growth of thin silicon films from hydrogenated silicon nanoparticles remain far from being understood. In the present work, extensive molecular dynamics simulations were performed to study the epitaxial growth of silicon thin films resulting from the deposition of plasma-born hydrogenated silicon clusters at low substrate temperatures under realistic reactor conditions. There is strong evidence that a temporary phase transition of the substrate area around the cluster impact site to the liquid state is necessary for the epitaxial growth to take place. We predict further that a non-normal incidence angle for the cluster impact significantly facilitates the epitaxial growth of thin crystalline silicon films.

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.

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.

Metallic-like bonding in plasma-born silicon nanocrystals for nanoscale bandgap engineering.

Based on ab initio molecular dynamics simulations, we show that small nanoclusters of about 1 nm size spontaneously generated in a low-temperature silane plasma do not possess tetrahedral structures, but are ultrastable. Apparently small differences in the cluster structure result in substantial modifications in their electric, magnetic, and optical properties, without the need for any dopants. Their non-tetrahedral geometries notably lead to electron deficient bonds that introduce efficient electron delocalization that strongly resembles the one of a homogeneous electron gas leading to metallic-like bonding within a semiconductor nanocrystal. As a result, pure hydrogenated silicon clusters that form by self-assembly in a plasma reactor possess optical gaps covering most of the solar spectrum from 1.0 eV to 5.2 eV depending simply on their structure and, in turn, on their degree of electron delocalization. This feature makes them ideal candidates for future bandgap engineering not only for photovoltaics, but also for many nano-electronic devices employing nothing else but silicon and hydrogen atoms.

A deeper insight into strain for the sila-bi[6]prismane ( Si18H12) cluster with its endohedrally trapped silicon atom, Si19H12.

A new family of over-coordinated hydrogenated silicon nanoclusters with outstanding optical and mechanical properties has recently been proposed. For one member of this family, namely the highly symmetric Si19 H12 nanocrystal, strain calculations have been presented with the goal to question its thermal stability and the underlying mechanism of ultrastability and electron-deficiency aromaticity. Here, the invalidity of these strain energy (SE) calculations is demonstrated mainly based on a fundamentally wrong usage of homodesmotic reactions, the miscounting of atomic bonds, and arithmetic errors. Since the article in question is entirely anchored on those erroneous SE values, all of its conclusions and predictions become without meaning. We provide evidence here that the nanocrystal in question suffers from such low levels of strain that its thermodynamical stability should be largely sufficient for device fabrication in a realistic plasma reactor. Most remarkably, the two "alternative," irregular isomers explicitly proposed in the aforementioned article are also electron-deficient, nontetrahedral, ultrastable, and aromatic nicely underlining the universality of the ultrastability concept for nanometric hydrogenated silicon clusters.

Temperature dependence of the radiative lifetimes in Ge and Si nanocrystals.

The effect of finite temperature on the optical properties of nanostructures has been a longstanding problem for their theoretical description and its omission presents serious limits on the validity of calculated spectra and radiative lifetimes. Most ab initio calculations have been carried out neglecting temperature effects altogether, although progress has been made recently. In the present work, the temperature dependence of the intrinsic radiative lifetimes of excited electron-hole pairs in Ge and Si nanocrystals due to classical temperature effects is calculated using ab initio molecular dynamics. Fully hydrogen-saturated Ge and Si nanocrystals without surface reconstructions show opposite behavior: the very short lifetimes in Ge increase with temperature, while the much longer ones in Si decrease. However, the temperature effect is found to be strongly dependent on the surface structure: surface reconstructions cause partial localization of the wave functions and override the difference between Si and Ge. As a consequence, the temperature dependence in reconstructed nanocrystals is strongly attenuated compared to the fully saturated nanocrystals. Our calculations are an important step towards predictive modeling of the optical properties of nanostructures.

Terahertz and gigahertz emission from an all-silicon nanocrystal.

Based on first-principles calculations, we predict the use of pure silicon nanocrystals as nano-oscillators in the giga- and terahertz region. Small- and large-amplitude, one-dimensional vibrations are observed. The former are spontaneously excited thermally at frequencies around 3 THz. Large-amplitude vibrations originate from oscillations between the inversion geometries of the nanocrystal and can be caused either classically by an external excitation or by quantum tunneling. The latter causes a ground-state splitting of 4.2 GHz, suggesting the use of the proposed nanocrystals as laser elements in a configuration analogous to that of the ammonia maser.

Electron-Deficiency Aromaticity in Silicon Nanoclusters.

Aromaticity in silicon-containing molecules has been a controversy for more than a century. Combining molecular dynamics simulations with ab initio calculations, we show here that it is possible to obtain aromatic-like behavior with pure hydrogenated silicon clusters without the need for multiple bonds. To this end, we exploit the natural tendency of silicon toward overcoordination to construct electron-deficient molecules with ring structures. Even without the incorporation of any protective bulky substituents the resulting structures are more stable than any other known hydrogenated silicon nanoparticles of this size and exhibit aromatic-like properties due to strong electron delocalization.

Ultrastable silicon nanocrystals due to electron delocalization.

We report a new nanocrystalline form of silicon that gives birth to pure hydrogenated silicon nanocrystals that absorb light in the ultraviolet, visible, and infrared spectral region despite their small size of only 1 nm and without the need for expensive or toxic metal atoms. On the basis of first-principles calculations, we demonstrate that those pure, but overcoordinated silicon nanocrystals are more stable than any other known silicon nanocrystals due to electron delocalization and that they form spontaneously via self-assembly. Therefore, we predict their immediate application in fields ranging from photovoltaic and light-emitting devices to photothermal cancer treatment.

Mechanically induced generation of highly reactive excited-state oxygen molecules in cluster scattering.

Molecular electronic excitation in (O(2))(n) clusters induced by mechanical collisions via the "chemistry with a hammer" is investigated by a combination of molecular dynamics simulations and quantum chemistry calculations. Complete active space self-consistent field augmented with triple-zeta polarizable basis set quantum chemistry calculations of a compressed (O(2))(2) cluster model in various configurations reveal the emergence of possible pathways for the generation of electronically excited singlet O(2) molecules upon cluster compression and vibrational excitation, due to electronic curve-crossing and spin-orbit coupling. Extrapolation of the model (O(2))(2) results to larger clusters suggests a dramatic increase in the population of electronically excited O(2) products, and may account for the recently observed cluster-catalyzed oxidation of silicon surfaces, via singlet oxygen generation induced by cluster impact, followed by surface reaction of highly reactive singlet O(2) molecules. Extensive molecular dynamics simulations of (O(2))(n) clusters colliding onto a hot surface indeed reveal that cluster compression is sufficient under typical experimental conditions for nonadiabatic transitions to occur. This work highlights the importance of nonadiabatic effects in the "chemistry with a hammer."

Deposition dynamics of hydrogenated silicon clusters on a crystalline silicon substrate under typical plasma conditions.

We have studied the deposition dynamics of hydrogenated silicon clusters on a silicon substrate for various cluster sizes and impact energies. The results show that the interaction processes of silicon nanocrystals with a crystalline silicon substrate strongly depend on the impact energy ranging from elastic scattering over soft-landing to cluster destruction with penetration of some cluster atoms into the substrate. Under certain conditions, epitaxial-like recrystallization of clusters has been observed after the initial cluster structure was completely lost upon surface impact. The reaction mechanisms as a function of impact energy are in good agreement with recent experimental results.

Nonadiabatic ladder climbing during molecular collisions.

Combining classical molecular dynamics simulations with high level, multiconfigurational ab initio calculations, we demonstrate that even relatively mild collisions between ground state oxygen molecules can readily lead to the formation of highly reactive singlet oxygen molecules via a novel "ladder climbing" mechanism. We employ our findings to shed some light on two recent experiments that have remained poorly understood until now. The first one concerns the highly efficient cluster-catalyzed etching of silicon surfaces, whereas the second one involves a yet to be explained "dark channel" observed for the ozone photolysis in the stratosphere.

Controlled growth of silicon nanocrystals in a plasma reactor.

Using a powerful multilevel simulation approach, we "visualize" the complete growth dynamics of hydrogenated silicon nanostructures under realistic experimental conditions of a plasma reactor. For the early stages of the synthesis, we demonstrate for the first time how precise control of atomic hydrogen not only permits one to choose between the production of amorphous and crystalline nanoparticles, but also to "steer" the growth toward the formation of elementary "building blocks" for the synthesis of hexagonal silicon nanowires.

Photodissociation of HCl and small (HCl)m complexes in and on large Ar n clusters.

Photodissociation experiments were carried out at 193 nm for single HCl molecules which are adsorbed on the surface of large Ar n clusters and small (HCl)m complexes which are embedded in the interior of these clusters. For the surface case the size dependence is measured for the average sizes n=140-1000. No cage exit events are observed in agreement with the substitutional position of the molecule deeply buried in the outermost shell. This result is confirmed by a molecular dynamics simulation of the pickup process under realistic conditions concerning the experiment and the interaction potentials. The calculations of the dissociation process employ the surface hopping model. For the embedded case the average sizes covered are m=3 and 6 and n=8-248. The kinetic energy of the H atom fragments is measured exhibiting peaks at zero and around 2.0 eV which mark completely caged and unperturbed fragments, respectively. The ratio of theses peaks strongly depends on the cluster size and agrees well with theoretical predictions for one and two closed icosahedral shells, in which the nonadiabatic coupling of all states was accounted for.

Musical quality assessment of clarinet reeds using optical holography.

Vibrational modes of 24 clarinet reeds have been observed in both dry and wet conditions using holographic interferometry. Results have been compared with the "musical quality" of the reeds as judged by two professional clarinet players. An excellent correspondence has been demonstrated between specific vibrational behavior and musical quality. The results suggest that the presence and symmetry of a strong first torsional mode are indicative of good or very good musical quality. A second, but less stringent quality criterion is the proximity of frequencies corresponding to the second torsional and the second flexural mode. This proximity leads to the creation of mixed vibrational modes for the very best of the investigated clarinet reeds.