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The stability of a mixture of two different surface reconstructions is investigated focusing on GaN(0001) surface mixed with Ga a d (2 × 2) and 3Ga-H(2 × 2) domains using the density functional theory calculations. Since the number of candidate structures is enormous, the structures sampled by Bayesian optimization are analyzed. As a result, the local electron counting (EC) rule alone was found to be insufficient to explain such stability. Then, augmenting the EC rule, a data-driven Ising model is proposed. The model allows the evaluation of the whole enormous number of candidate structures. The approach is expected to be useful for theoretical studies of such mixtures on various semiconductor surfaces. [ABSTRACT FROM AUTHOR]

Ab initio simulations were applied for nonpolar GaN/AlN superlattices of various widths for the first time giving band diagrams and optical transition oscillator strengths. The results confirmed the absence of electric fields in m-plane GaN/AlN multiquantum well (MQW) systems leading to drastically different properties of polar and nonpolar systems, narrow polar and nonpolar GaN/AlN well properties, such as bandgap or oscillator strength. Wider wells show drastic differences related to the presence of electric fields in polar systems. Wide nonpolar wells have bandgaps following parabolic dependence resulting from localization energy. Polar wide well gaps are determined by spontaneous and piezoelectric fields that reduce bandgap for wider wells and barriers. Oscillator strength shows a more dramatic difference between polar and nonpolar wells. Drastic reduction in the oscillator strength is observed for wide polar MQWs. The decrease in the oscillator strength by several orders of magnitude is observed for the increase in the width of wells and barriers. The wide polar wells should have extremely ineffective radiative emission from both direct and across the barrier overlap of electron–hole wavefunctions. [ABSTRACT FROM AUTHOR]

It is shown that charge transfer, the process analogous to formation of semiconductor p-n junction, contributes significantly to adsorption energy at semiconductor surfaces. For the processes without the charge transfer, such as molecular adsorption of closed shell systems, the adsorption energy is determined by the bonding only. In the case involving charge transfer, such as open shell systems like metal atoms or the dissociating molecules, the energy attains different value for the Fermi level differently pinned. The Density Functional Theory (DFT) simulation of species adsorption at different surfaces, such as SiC(0001) or GaN(0001) confirms these predictions: the molecular adsorption is independent on the coverage, while the dissociative process adsorption energy varies by several electronvolts. [ABSTRACT FROM AUTHOR]

Semiconductor surfaces were divided into charge categories, i.e., surface acceptor, donor, and neutral ones that are suitable for simulations of their properties within a slab model. The potential profiles, close to the charged surface states, accounting for explicit dependence of the point defects energy, were obtained. A termination charge slab model was formulated and analyzed proving that two control parameters of slab simulations exist: the slope and curvature of electric potential profiles which can be translated into a surface and volumetric charge density. The procedures of slab model parameter control are described and presented using examples of the DFT simulations of GaN and SiC surfaces showing the potential profiles, linear or curved, depending on the band charge within the slab. It was also demonstrated that the field at the surface may affect some surface properties in a considerable degree proving that verification of this dependence is obligatory for a precise simulation of the properties of semiconductor surfaces. [ABSTRACT FROM AUTHOR]

Chemical adsorption of the species at semiconductor surfaces is analyzed showing the existence of the two contributions to adsorption energy: bond creation and charge transfer. It is shown that the energy of quantum surface states is affected by the electric field at the surface, nevertheless, the potential contribution of electron and nuclei cancels out. The charge transfer contribution is Fermi level independent for pinned surfaces. Thus for Fermi level pinned at the surface, the adsorption energy is independent on the Fermi energy, i.e., the doping in the bulk. The DFT simulations of adsorption of hydrogen at clean GaN(0001) and silicon at SiC(0001) surfaces confirmed independence of adsorption energy on the doping in the bulk. For the Fermi level nonpinned surfaces, the charge contribution depends on the position of Fermi level in the bulk. Thus adsorption energy is sensitive to change of the Fermi energy in the bulk, i.e., the doping. The DFT simulations of adsorption of atomic hydrogen at 0.75 ML hydrogen covered GaN(0001) surface confirmed that the adsorption energy may be changed by about 2 eV by the doping change from n- to p-type. [ABSTRACT FROM AUTHOR]

Laplace correction was used for solutions of Poisson equation in density functional theory (DFT) slab simulations of GaN (0001) surface. In accordance to the scenario of Meyer and Marx [Phys. Rev. B 67, 35403 (2003)], the electric field, emerging within the slab, is determined by the condition that Fermi energy is equal to the energies of valence band maximum and conduction band minimum at both sides of the slab. In contrast to their predictions that the field is identical for different slab thicknesses, it was found from DFT calculations that the electric potential difference between two sides of the slab is kept constant. Therefore, the energy of the slab does not diverge for large slab thickness. It was also found that, in most cases, the field in the slab is determined by pinning by surface states. Thus the change in opposite side slab termination, both by different types of atoms and by their location, can be used to change electric field in the slab, creating a tool that can be used to simulate the change in surface properties due to doping of the bulk. It was shown that, depending on the electric field, the energy of surface states changes in the way different from the band states. This change could be large, comparable to the bandgap. Despite the fact that the Fermi energy can be pinned to surface states, it may change its energy with respect to valence band and conduction band as a function of the doping of bulk semiconductor. These results are in agreement with the experimental data showing variation in Fermi energy at the GaN (0001) surface in function of the doping in the bulk. It was also shown using the electron density and potential profiles that ten Ga–N atomic layers are necessary to achieve small quantum overlap of the surface states of both sides of the slab, which is required for high precision simulations of the surface. [ABSTRACT FROM AUTHOR]

It is proved that in slab simulations of uniform semiconductor surfaces the electric field in the vacuum space should vanish. In standard approach this condition was achieved by introduction of the dipole correction [J. Neugebauer and M. Scheffler, Phys. Rev. B 46, 16067 (1992)]. An effective and stable method of exact solution of Poisson equation, based on Laplace correction, which attains the zero field condition in the vacuum, is described. The dipole correction to the slab energy is removed. Additionally, a method of the control of electric field within the slab is introduced, applicable in direct simulations of Fermi level influence on the properties of semiconductor surfaces. [ABSTRACT FROM AUTHOR]

GaN (0001) surface in an ammonia-rich vapor ambient, typical for ammonia annealing, metalo-organic vapor phase epitaxy (MOVPE) or hydride vapor phase epitaxy (HVPE) was considered. It was shown that, in these three cases, the stationary state of the surface corresponds to condition far from equilibrium. The chemical potential of nitrogen and hydrogen at the surface was determined using kinetic arguments, i.e., derived form the magnitude of flux of ammonia. For HVPE and MOVPE growth, the chemical potential of gallium depends on the distance from the steps. Thus, only far distance from the step value of the gallium chemical potential at the GaN(0001) surface could be determined in similar way. In the alternative case of GaN annealing in ammonia atmosphere, gallium chemical potential at the surface remains undetermined (the surface is in a metastable state). Additionally, using thermodynamic arguments, the limits for the chemical potential of gallium (upper) and nitrogen (lower) were formulated for the case of vapor growth, and expressed as functions of temperature and pressure. The results, regarding the atomic processes on the GaN(0001) surface, were obtained using the SIESTA, density functional theory based code, and consequently employed in the comparable thermodynamic and kinetic analysis of the state of GaN(0001) surface. [ABSTRACT FROM AUTHOR]

Adsorption of ammonia at NH3/NH2/H-covered GaN(0001) surface was analyzed using results of ab initio calculations. The whole configuration space of partially NH3/NH2/H-covered GaN(0001) surface was divided into zones of differently pinned Fermi level: at the Ga broken bond state for dominantly bare surface (region I), at the valence band maximum (VBM) for NH2 and H-covered surface (region II), and at the conduction band minimum (CBM) for NH3-covered surface (region III). The electron counting rule (ECR) extension was formulated for the case of adsorbed molecules. The extensive ab intio calculations show the validity of the ECR in case of all mixed H-NH2-NH3 coverages for the determination of the borders between the three regions. The adsorption was analyzed using the recently identified dependence of the adsorption energy on the charge transfer at the surface. For region I ammonia adsorbs dissociatively, disintegrating into a H adatom and a HN2 radical for a large fraction of vacant sites, while for region II adsorption of ammonia is molecular. The dissociative adsorption energy strongly depends on the Fermi level at the surface (pinned) and in the bulk (unpinned) while the molecular adsorption energy is determined by bonding to surface only, in accordance to the recently published theory. Adsorption of Ammonia in region III (Fermi level pinned at CBM) leads to an unstable configuration both molecular and dissociative, which is explained by the fact that broken Ga-bonds are doubly occupied by electrons. The adsorbing ammonia brings 8 electrons to the surface, necessitating the transfer of these two electrons from the Ga broken bond state to the Fermi level. This is an energetically costly process. Adsorption of ammonia at H-covered site leads to the creation of a NH2 radical at the surface and escape of H2 molecule. The process energy is close to 0.12 eV, thus not large, but the direct inverse process is not possible due to the escape of the hydrogen molecule. [ABSTRACT FROM AUTHOR]

Recently developed model allows for simulations of electric field influence on the surface states. The results of slab simulations show considerable change of the energy of quantum states in the electric field, i.e., Stark Effect associated with the surface (SSSE-Surface States Stark Effect). Detailed studies of the GaN slabs demonstrate spatial variation of the conduction and valence band energy revealing real nature of SSSE phenomenon. It is shown that long range variation of the electric potential is in accordance with the change of the energy of the conduction and valence bands. However, at short distances from GaN(0001) surface, the valence band follows the potential change while the conduction states energy is increased due to quantum overlap repulsion by surface states. It is also shown that at clean GaN(0001) surface Fermi level is pinned at about 0.34 eV below the long range projection of the conduction band bottom and varies with the field by about 0.31 eV due to electron filling of the surface states. [ABSTRACT FROM AUTHOR]