We have studied diffusion pathways of a silyl radical adsorbed on the hydrogenated Si (100)-(2x1) surface by density-functional theory. The process is of interest for the growth of crystalline silicon by plasma-enhanced chemical vapor deposition. Preliminary searches for migration mechanisms have been performed using metadynamics simulations. Local minima and transition states have been further refined by using the nudged-elastic-band method. Barriers for diffusion from plausible adsorption sites as low as 0.2 eV have been found, but trap states have also been spotted, leading to a more stable configuration, with escape barriers of 0.7 eV. Diffusion among weakly bound physisorbed states is also possible with very low activation barriers (<50 meV). However, desorption mechanisms (either as SiH3 or as SiH4) from physisorbed or more strongly bound adsorption configurations turn out to have activation energies similar to diffusion barriers. Kinetic Monte Carlo simulations based on ab initio activation energies show that the silyl radical diffuses at most by a few lattice spacing before desorbing at temperatures in the range 300-1000 K.
We report first principles ab initio density functional calculations of hydrogen dynam- ics in hydrogenated amorphous silicon. Thermal motion of the host Si atoms drives H diffusion, as we demonstrate by direct simulation and explain with simple models. Si-Si bond centers and Si ring centers are local energy minima as expected. We also describe a new mechanism for break- ing Si-H bonds to release free atomic H into the network: a fluctuation bond center detachment (FBCD) assisted diffusion. H dynamics in a-Si:H is dominated by structural fluctuations intrinsic to the amorphous phase not presen…
The present research work is focused on the effect of activation procedure on the hydrogen absorption-desorption properties of new rare earth transition metal compound based on Sm(Co0.6Fe0.2Zr0.16B0.04)7.5 composition. Crystal structure and composition is always connected to the maximum capacity of the intermetallic hydrides. For composite materials the thermodynamic properties of hydrogenation & dehydrogenation procedure are mostly explained through microstructure-microchemistry characteristics. Efficient hydrogen storage is direct connected to the desorbed hydrogen amount. The as hydrogenate…
The adsorbate dynamics during simultaneous action of desorption and lateral adsorbate diffusion is studied in a simple lattice-gas model by kinetic Monte Carlo simulations. It is found that the action of the coverage-conserving diffusion process during the course of the desorption has two distinct, competing effects: a general acceleration of the desorption process, and a coarsening of the adsorbate configuration through Ostwald ripening. The balance between these two effects is governed by the structure of the adsorbate layer at the beginning of the desorption process.
The dynamics of desorption from a submonolayer of adsorbed atoms or ions are significantly influenced by the absence or presence of lateral diffusion of the adsorbed particles. When diffusion is present, the adsorbate configuration is simultaneously changed by two distinct processes, proceeding in parallel: adsorption/desorption, which changes the total adsorbate coverage, and lateral diffusion, which is coverage conserving. Inspired by experimental results, we here study the effects of these competing processes by kinetic Monte Carlo simulations of a simple lattice-gas model. In order to unta…
Evaluation of hydrogen diffusion and trapping in ferritic steels containing (Ti,Cr)C particles using electrochemical permeation and thermal desorption spectroscopy
We report a first principles study of the structure and the vibrational properties of the Si(100)-H(2 \times 1) surface in an electric field. The calculated vibrational parameters are used to model the vibrational modes in the presence of the electric field corresponding to a realistic STM tip-surface geometry. We find that local one-phonon excitations have short lifetimes (10 ps at room temperature) due to incoherent lateral diffusion, while diffusion of local multi-phonon excitations are suppressed due to anharmonic frequency shifts and have much longer lifetimes (10 ns at room temperature).…
We present a study of the dynamical behavior of a Ziff-Gulari-Barshad model with CO desorption and lateral diffusion. Depending on the values of the desorption and diffusion parameters, the system presents a discontinuous phase transition between low and high CO coverage phases. We calculate several points on the coexistence curve between these phases. Inclusion of the diffusion term produces a significant increase in the CO_2 production rate. We further applied a square-wave periodic pressure variation of the partial CO pressure with parameters that can be tuned to modify the catalytic activi…
The release of a gas limited by surface desorption, or by diffusion from the bulk of spherical pebbles is revisited. A method is proposed to identify the release limiting process, by comparing a partial temperature ramp, up to slightly beyond the release peak, followed by a rapid temperature drop, to a second, full release ramp. Comparing the release curve from the second ramp to that of the first one: i) the peak is unmoved in first order desorption kinetics, and moves to higher temperature in the other cases, ii) as compared to the Arrhenius analysis of the first curve, that of the second is…
Study of helium diffusion in yttria: A multiscale approach based on the density functional theory and kinetic Monte Carlo, with transmission electron microscopy and thermo-desorption spectroscopy
A current series of papers on barrier-controlled and trapping processes in solids and/or at solid surfaces have laid down the emphasis onto describing the statistical event by means of the barrier currents method due to Bardeen and Christov. The present study centered on photodesorption and photoelectrification is the fourth of an arXiv series which also included rapid statistical approaches to nucleation, diffusion and drift currents in state of the art materials. We presently extend our arguments to spherical square and oscillatory wells to deal with the photoprocesses.
We present a first-principles study of native defects in NaAlH$_4$. Our analysis indicates that the structure and energetics of these defects can be interpreted in terms of elementary building blocks, which include $V_{\rm{AlH_4}}^+$, $V_{\rm{Na}}^-$, $V_{\rm{H}}^+$, H$_i^-$, and (H$_2$)$_i$. We also calculate migration barriers for several key defects, in order to compare enthalpies of diffusion to experimentally measured activation energies of desorption. From this, we estimate activation energies for diffusion of defects and defect pairs. We suggest that $V_{\rm{AlH_4}}^+$ and H$_i^-$, or $…
First-principle density-functional calculations have been applied to study the interaction of molecular chlorine with the (111) plane of copper. Using transition-state search method, we considered the elementary processes (Cl$_2$ dissociation, adsorption, diffusion, association and desorption) on the chlorinated Cu(111) surface. A systematic study of possible desorption pathways has been carried out for different species (Cl, Cl$_2$, CuCl, CuCl$_2$, and Cu) at various chlorine coverage. As a result, we concluded that chlorine monolayer irrespective of the coverage desorbs in the form of CuCl m…
The propagation of sidewall steps during the growth of nanowires is calculated in the frame of the Burton-Cabrera-Frank model. The stable shape of the nanowire comprises a cylinder section on top of a cone section: their characteristics are obtained as a function of the radius of the catalyst-nanowire area, the desorption-limited diffusion length of adatoms on the terraces, and the sticking of adatoms at step edges. The comparison with experimental data allows us to evaluate these last two parameters for InP and ZnTe nanowires; it reveals a different behavior for the two materials, related to …
Zeolite channels can be used as effective hydrocarbon traps. Earlier experiments (Czaplewski {\sl et al.}, 2002) show that the presence of large aromatic molecules (toluene) block the diffusion of light hydrocarbon molecules (propane) inside the narrow pore of a zeolite sample. As a result, the desorption temperature of propane is significantly higher in the binary mixture than in the single component case. In order to obtain further insight into these results, we use a simple lattice gas model of diffusion of hard-core particles to describe the diffusive transport of two species of molecules …
Step meandering due to a deterministic morphological instability on vicinal surfaces during growth is studied. We investigate nonlinear dynamics of a step model with asymmetric step kinetics, terrace and line diffusion, by means of a multiscale analysis. We give the detailed derivation of the highly nonlinear evolution equation on which a brief account has been given [Pierre-Louis et.al. PRL(98)]. Decomposing the model into driving and relaxational contributions, we give a profound explanation to the origin of the unusual divergent scaling of step meander ~ 1/F^{1/2} (where F is the incoming a…
Balancing Thermodynamics, Kinetics, and Reversibility in Ti-Doped MgB2H8: A First-Principles Assessment of a Practical Solid-State Hydrogen Storage Material
New Technologies Research Center, University of West Bohemia（新技研究中心，西波希米亚大学）；Department of Physics, Bacha Khan University（巴哈汗大学物理系）
Oscillatory Zoning (OZ) is a phenomenon exhibited by many geologically formed crystals. It is characterized by quasi periodic oscillations in the composition of a solid solution, caused by self-organization. We present a new model for OZ. The growth mechanism applied includes species diffusion through the solution bulk, particle adsorption, surface diffusion and subsequently desorption or incorporation into the crystal. This mechanism, in particular, can provide the synchronization effects necessary to reproduce the layered structure of experimentally obtained crystals, lacking in other models…
Polaron-mediated metal-insulator transition and proton conduction in hydrogenated nickelate perovskites
School of Physics and Astronomy, Beijing Normal University（北京师范大学物理学院）；Key Laboratory of Multiscale Spin Physics (Beijing Normal University), Ministry of Education（教育部多尺度自旋物理重点实验室（北京师范大学））；College of Physics, Hebei Normal University（河北师范大学物理学院）；Hebei Advanced Thin Films Laboratory（河北省先进薄膜实验室）
Generalized Phase Diagrams for Graphene CVD growth on Copper
National Laboratory of Solid State Microstructures（固体微结构物理国家重点实验室）；School of Physics, Nanjing University（南京大学物理学院）；Collaborative Innovation Center of Advanced Microstructures（先进结构协同创新中心）
The inability to grow large well ordered graphene with a specific number of layers on SiC(0001) is well known. The growth involves several competing processes (Si desorption, carbon diffusion, island nucleation etc.), and because of the high temperatures, it has not been possible to identify the growth mechanism. Using Scanning tunneling microscopy and an initially vicinal 6H-SiC(0001) sample, we determine the sequence of microscopic processes that result in the formation of bilayer graphene. Adjacent steps retract with different speeds and the carbon released produces characteristic "fingers"…
We present dynamic Monte Carlo simulations of a lattice-gas model for bromine electrodeposition on single-crystal silver (100). This system undergoes a continuous phase transition between a disordered phase at low electrode potentials and a commensurate c(2X2) phase at high potentials. The lattice-gas parameters are determined by fitting simulated equilibrium adsorption isotherms to chronocoulometric data, and free-energy barriers for adsorption/desorption and lateral diffusion are estimated from ab initio data in the literature. Cyclic voltammograms in the quasi-static limit are obtained by e…
Controlling the contamination of silicon materials by iron, especially dissolved interstitial iron (Fe$_{\mathrm{i}}$), is a longstanding problem with recent developments and several open issues. Among these we have the question whether hydrogen can assist iron diffusion, or if significant amounts of substitutional iron (Fe$_{\mathrm{s}}$) can be created. Using density functional calculations we explore the structure, formation energies, binding energies, migration, and electronic levels of several FeH complexes in Si. We find that a weakly bound Fe$_{\mathrm{i}}$H pair has a migration barrier…
We investigate the influence of step edge diffusion (SED) and desorption on Molecular Beam Epitaxy (MBE) using kinetic Monte-Carlo simulations of the solid-on-solid (SOS) model. Based on these investigations we propose two strategies to optimize MBE growth. The strategies are applicable in different growth regimes: During layer-by-layer growth one can exploit the presence of desorption in order to achieve smooth surfaces. By additional short high flux pulses of particles one can increase the growth rate and assist layer-by-layer growth. If, however, mounds are formed (non-layer-by-layer growth…
The influence of nearest-neighbor diffusion on the decay of a metastable low-coverage phase (monolayer adsorption) in a square lattice-gas model of electrochemical metal deposition is investigated by kinetic Monte Carlo simulations. The phase-transformation dynamics are compared to the well-established Kolmogorov-Johnson-Mehl-Avrami theory. The phase transformation is accelerated by diffusion, but remains in accord with the theory for continuous nucleation up to moderate diffusion rates. At very high diffusion rates the phase-transformation kinetic shows a crossover to instantaneous nucleation…
