Gueorgui Kostov Gueorguiev

Van der Waals stacks of few-layer h-AlN with graphene: an ab initio study of structural, interaction and electronic properties.

Graphite-like hexagonal AlN (h-AlN) multilayers have been experimentally manifested and theoretically modeled. The development of any functional electronics applications of h-AlN would most certainly require its integration with other layered materials, particularly graphene. Here, by employing vdW-corrected density functional theory calculations, we investigate structure, interaction energy, and electronic properties of van der Waals stacking sequences of few-layer h-AlN with graphene. We find that the presence of a template such as graphene induces enough interlayer charge separation in h-AlN, favoring a graphite-like stacking formation. We also find that the interface dipole, calculated per unit cell of the stacks, tends to increase with the number of stacked layers of h-AlN and graphene.

Exploring hydrogenation and fluorination in curved 2D carbon systems: a density functional theory study on corannulene.

Corannulene has been a useful prototype for studying C-based nanostructures as well as surface chemistry and reactivity of sp(2)-hybridized carbon-based materials. We have investigated fluorination and hydrogenation of corannulene carrying out density functional theory calculations. In general, the fluorination is energetically more favorable than hydrogenation of corannulene. The substitution of the peripheral H atoms in the corannulene molecule by F atoms leads to a larger cohesive energy gain than when F (or H) atoms are bonded to the hub carbon and bridge carbon sites of this molecule. As expected for doped C-based nanostructures, the hydrogenation or fluorination significantly changes the HOMO-LUMO gap of the system. We have obtained HOMO-LUMO gap variations of 0.13-3.46 eV for F-doped and 0.38-1.52 eV for H-doped systems. These variations strongly depend on the concentration and position of the incorporated F/H atoms, instead of the structural stability of the doped systems. Considering these calculations, we avoid practical difficulties associated with the addition/substitution reactions of larger curved two-dimensional (2D) carbon nanostructures, and we obtain a comprehensive and systematic understanding of a variety of F/H 2D doped systems.

Silicon and metal nanotemplates: Size and species dependence of structural and electronic properties

We utilize first-principles computer simulations to study the dependence on size (n) and species (M) of structural and electronic properties of clusters with stoichiometry M Sin. We investigate a total of 168 clusters comprising from 1 to 14 silicon atoms together with one transition metal atom among 12 different elements. It is found that all elements exhibit a very similar size-dependence for the cohesive energy, in which clusters with n=7, 12 appear as local maxima, with shapes which are found to be essentially independent of the transition metal atom. It is also found that the electronic properties of structurally equivalent clusters depend sensitively on the transition metal atom involved, providing the means to tailor specific properties when designing cluster assembled materials.

Effect of impurity incorporation on crystallization in AlN sublimation epitaxy

We have implemented graphite, graphite-tantalum (Ta), and Ta growth environment to the sublimation epitaxy of aluminum nitride (AlN) and have studied development, morphological, and cathodoluminescence emission properties of AlN crystallites. Three apparently different types of crystallites form in the three different types of growth environment, which presumably manifests the relationship between crystallite-habit-type and impurities. Comparison between the cathodoluminescence spectra reveals certain dynamics in the incorporation into AlN of the main residual dopants, oxygen and carbon, when the growth environment changes. At high temperatures, in addition to Al and N2, which constitute the vapor over AlN, vapor molecules of CN, NO, Al2C, and many more can be present in the vapor from which AlN grows and both oxygen and carbon can be incorporated into AlN in varying ratios. Involving calculations of the cohesive energy per atom of such vapor molecules and also of Ta containing molecules, we have consider...

Spin-orbit-induced gap modification in buckled honeycomb XBi and XBi3 (X = B, Al, Ga, and In) sheets

The band structure and stability of XBi and XBi3 (X  =  B, Al, Ga, and In) single sheets are predicted using first-principles calculations. It is demonstrated that the band gap values of these new classes of two-dimensional (2D) materials depend on both the spin-orbit coupling (SOC) and type of group-III elements in these hetero-sheets. Thus, topological properties can be achieved, allowing for viable applications based on coherent spin transport at room temperature. The spin-orbit effects are proved to be essential to explain the tunability by group-III atoms. A clear effect of including SOC in the calculations is lifting the spin degeneracy of the bands at the Γ point of the Brillouin zone. The nature of the band gaps, direct or indirect, is also tuned by SOC, and by the appropriate X element involved. It is observed that, in the case of XBi single sheets, band inversions naturally occur for GaBi and InBi, which exhibit band gap values around 172 meV. This indicates that these 2D materials are potential candidates for topological insulators. On the contrary, a similar type of band inversion, as obtained for the XBi, was not observed in the XBi3 band structure. In general, the calculations, taking into account SOC, reveal that some of these buckled sheets exhibit sizable gaps, making them suitable for applications in room-temperature spintronic devices.

Structural and Mechanical Properties of CNx and CPx Thin Solid Films

The inherent resiliency, hardness and relatively low friction coefficient of the fullerene-like (FL) allotrope of carbon nitride (CNx) thin solid films give them potential in numerous tribological applications. In this work, we study the substitution of N with P to grow FL-CPx to achieve better cross- and inter-linking of the graphene planes, improving thus the material’s mechanical and tribological properties. The CNx and CPx films have been synthesized by DC magnetron sputtering. HRTEM have shown the CPx films exhibit a short range ordered structure with FL characteristics for substrate temperature of 300 °C and for a phosphorus content of 10-15 at.%. These films show better mechanical properties in terms of hardness and resiliency compared to those of the FL-CNx films. The low water adsorption of the films is correlated to the theoretical prediction for low density of dangling bonds in both, CNx and CPx. First-principles calculations based on Density Functional Theory (DFT) were performed to provide additional insight on the structure and bonding in CNx, CPx, and a-C compounds.

Dopant species with Al–Si and N–Si bonding in the MOCVD of AlN implementing trimethylaluminum, ammonia and silane

We have investigated gas-phase reactions driven by silane (SiH4), which is the dopant precursor in the metalorganic chemical vapor deposition (MOCVD) of aluminum nitride (AlN) doped by silicon, with prime focus on determination of the associated energy barriers. Our theoretical strategy is based on combining density-functional methods with minimum energy path calculations. The outcome of these calculations is suggestive for kinetically plausible and chemically stable reaction species with Al–Si bonding such as (CH3)2AlSiH3 and N–Si bonding such as H2NSiH3. Within this theoretical perspective, we propose a view of these reaction species as relevant for the actual MOCVD of Si-doped AlN, which is otherwise known to be contributed by the reaction species (CH3)2AlNH2 with Al–N bonding. By reflecting on experimental evidence in the MOCVD of various doped semiconductor materials, it is anticipated that the availability of dopant species with Al–Si, and alternatively N–Si bonding near the hot deposition surface, can govern the incorporation of Si atoms, as well as other point defects, at the AlN surface.

Synthesis and properties of CS x F y thin films deposited by reactive magnetron sputtering in an Ar/SF6 discharge

A theoretical and experimental study on the growth and properties of a ternary carbon-based material, CS x F y , synthesized from SF6 and C as primary precursors is reported. The synthetic growth concept was applied to model the possible species resulting from the fragmentation of SF6 molecules and the recombination of S-F fragments with atomic C. The possible species were further evaluated for their contribution to the film growth. Corresponding solid CS x F y thin films were deposited by reactive direct current magnetron sputtering from a C target in a mixed Ar/SF6 discharge with different SF6 partial pressures ([Formula: see text]). Properties of the films were determined by x-ray photoelectron spectroscopy, x-ray reflectivity, and nanoindentation. A reduced mass density in the CS x F y films is predicted due to incorporation of precursor species with a more pronounced steric effect, which also agrees with the low density values observed for the films. Increased [Formula: see text] leads to decreasing deposition rate and increasing density, as explained by enhanced fluorination and etching on the deposited surface by a larger concentration of F/F2 species during the growth, as supported by an increment of the F relative content in the films. Mechanical properties indicating superelasticity were obtained from the film with lowest F content, implying a fullerene-like structure in CS x F y compounds.

Kinetics of residual doping in 4H-SiC epitaxial layers grown in vacuum

Investigation on residual Al, B, and N co-doping of 4H-SiC epitaxial layers is reported. The layers were produced by sublimation epitaxy in Ta growth cell environment at different growth temperatures and characterized by secondary ion mass spectrometry. The vapor interaction with Ta was considered through calculations of cohesive energies of several Si-, Al-, B-, and N-containing vapor molecules and also of diatomic Ta–X molecules. An analysis of kinetic mechanisms responsible for impurity incorporation is performed. Among residuals, B exhibits a stronger incorporation dependence on temperature and growth at lower temperatures can favor B decrease in the layers. Under the growth conditions in this study (Ta environment and presence of attendant Al and N), B incorporation is assisted by Si2C vapor molecule. Boron tends to occupy carbon sites at higher temperatures, i.e. higher growth rates.

Self-Healing in Carbon Nitride Evidenced As Material Inflation and Superlubric Behavior

All known materials wear under extended mechanical contacting. Superlubricity may present solutions, but is an expressed mystery in C-based materials. We report negative wear of carbon nitride films; a wear-less condition with mechanically induced material inflation at the nanoscale and friction coefficient approaching ultralow values (0.06). Superlubricity in carbon nitride is expressed as C-N bond breaking for reduced coupling between graphitic-like sheets and eventual N2 desorption. The transforming surface layer acts as a solid lubricant, whereas the film bulk retains its high elasticity. The present findings offer new means for materials design at the atomic level, and for property optimization in wear-critical applications like magnetic reading devices or nanomachines.