Pawel Kempisty

Fermi level influence on the adsorption at semiconductor surfaces—ab initio simulations

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 hy...

Foundations of ab initio simulations of electric charges and fields at semiconductor surfaces within slab models

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...

Fermi level pinning and the charge transfer contribution to the energy of adsorption at semiconducting surfaces

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.

Principal physical properties of GaN/AlN multiquantum well systems determined by density functional theory calculations

A critical comparison of three polarization based approaches with the fields in AlN/GaN multiple quantum wells (MQWs) systems proved that they give identical results. The direct density functional theory (DFT) results, i.e., the fields, are in qualitative agreement with data obtained within the polarization theory. The results of DFT calculations of an AlN/GaN MQW system were used in the projection method to obtain a spatial distribution of the bands in the structure with atomic resolution. In parallel, the plane averaged and c-smoothed potential profiles obtained from the solution of the Poisson equation were used to determine the electric field in the multiquantum well structures and the magnitude of dipole layers at the AlN/GaN heterostructures. The dipole layers cause potential jumps of about 2.4 V that seriously affects the band offsets. The presence of the dipole layer is in good agreement with the potential measurements by electron holography. It was shown that the wells of the width up to 4 Ga lay...

General aspects of the vapor growth of semiconductor crystals – A study based on DFT simulations of the NH3/NH2 covered GaN(0001) surface in hydrogen ambient

Abstract Vapor growth of semiconductors is analyzed using recently obtained dependence of the adsorption energy on the electron charge transfer between the surface adsorbed species and the bulk [Krukowski et al. J. Appl. Phys. 114 (2013) 063507, Kempisty et al. ArXiv1307.5778 (2013)]. Ab initio calculations were performed to study the physical properties of GaN(0001) surface in ammonia-rich conditions, i.e. covered by mixture of NH3 molecules and NH2 radicals. The Fermi level is pinned at valence band maximum (VBM) and conduction band minimum (CBM) for full coverage by NH3 molecules and NH2 radicals, respectively. For the crossover content of ammonia of about 25% monolayer (ML), the Fermi level is unpinned. It was shown that hydrogen adsorption energy depends on the doping in the bulk for the unpinned Fermi level, i.e. for this coverage. Surface structure thermodynamic and mechanical stability criteria are defined and compared. Mechanical stability of the coverage of such surfaces was checked by determination of the desorption energy of hydrogen molecules. Thermodynamic stability analysis indicates that initially equilibrium hydrogen vapor partial pressure steeply increases with NH3 content to attain the crossover NH3/NH2 coverage, i.e. the unpinned Fermi level condition. For such condition the entire range of experimentally accessible pressures belongs showing that vapor growth of semiconductor crystals occurs predominantly for unpinned Fermi level at the surface, i.e. for flat bands. Accordingly, adsorption energy of most species depends on the doping in the bulk that is based on the possible molecular scenario explaining dependence of the growth and the doping of semiconductor crystals on the doping in the bulk.

Erratum to “Ab initio determination of atomic structure and energy of surface states of bare and hydrogen covered GaN (0001) surface — Existence of the Surface States Stark Effect (SSSE)” [Surf. Sci. 605 (2011) 695-713]

We obtained new nonrelativistic expression for the dynamical van der Waals atom -surface interaction energy of very convenient form for different applications. It is shown that classical result (Ferrell and Ritchie, 1980) holds only for a very slowly moving atom. In general case, the van der Waals atom -surface interaction energy manifests strong nonlinear dependence on velocity and distance. In close vicinity of metal and dielectric surfaces and velocities from 1 to 10 Bohr units the dynamical van der Waals potential proves to be significantly lower that in static case and goes to the static values with increasing distance and (or) decreasing velocity.

Structural and electronic properties of AlN(0001) surface under partial N coverage as determined by ab initio approach

Properties of bare and nitrogen-covered Al-terminated AlN(0001) surface were determined using density functional theory (DFT) calculations. At a low nitrogen coverage, the Fermi level is pinned by Al broken bond states located below conduction band minimum. Adsorption of nitrogen is dissociative with an energy gain of 6.05 eV/molecule at a H3 site creating an overlap with states of three neighboring Al surface atoms. During this adsorption, electrons are transferred from Al broken bond to topmost N adatom states. Accompanying charge transfer depends on the Fermi level. In accordance with electron counting rule (ECR), the DFT results confirm the Fermi level is not pinned at the critical value of nitrogen coverage θN(1) = 1/4 monolayer (ML), but it is shifted from an Al-broken bond state to Npz state. The equilibrium thermodynamic potential of nitrogen in vapor depends drastically on the Fermi level pinning being shifted by about 4 eV for an ECR state at 1/4 ML coverage. For coverage above 1/4 ML, adsorptio...

Ab initio study of Ga-GaN system: Transition from adsorbed metal atoms to a metal–semiconductor junction

Ab initio studies of a GaN(0001)-Ga system with various thicknesses of a metallic Ga layer were undertaken. The studied systems extend from a GaN(0001) surface with a fractional coverage of gallium atoms to a Ga-GaN metal–semiconductor (m–s) contact. Electronic properties of the system are simulated using density functional theory calculations for different doping of the bulk semiconductor. It is shown that during transition from a bare GaN(0001) surface to a m–s heterostructure, the Fermi level stays pinned at a Ga-broken bond highly dispersive surface state to Ga–Ga states at the m–s interface. Adsorption of gallium leads to an energy gain of about 4 eV for a clean GaN(0001) surface and the energy decreases to 3.2 eV for a thickly Ga-covered surface. The transition to the m–s interface is observed. For a thick Ga overlayer such interface corresponds to a Schottky contact with a barrier equal to 0.9 and 0.6 eV for n- and p-type, respectively. Bond polarization-related dipole layer occurring due to an ele...

Discretization of the Drift-Diffusion Equations with the Composite Discontinuous Galerkin Method

We present three variants of discretization of the stationary van Roosbroeck equations. They are the Composite Discontinuous Galerkin Methods, in standard symmetric/non-symmetric version, and the Weakly Over-Penalized Symmetric Interior Penalty method.