Electronic and Structural Properties of the Ge/GeO2 Interface through Hybrid Functionals

The performance of silicon based microelectronic circuits reaches the end of the roadmap. New material systems are required for further improvements in speed and power consumption. Germanium is a possible candidate to substitute silicon for microelectronic devices. Its hole mobility is the highest of all semiconductor materials. Together with its lower band gap it could be an ideal material for energy-saving devices. This thesis is dedicated to first principles studies of the Ge/GeO2 interface through hybrid density functional theory. The substoichiometric region of the interface is of special interest. A wide substoichiometric region is supported by total energy calculations of a set of crystalline model systems. An unexpected structure organization was found through molecular dynamics simulations of substoichiometric GeO. We found that a majority of germanium and oxygen atoms are threefold coordinated, forming valence alternation pairs (VAPs). A detailed energetic analysis located the VAPs in the low-oxygen region of the interface. VAPs show interesting properties : They are prone to charge trapping. The electron trapping level might explain the bad performance of n-type doped devices. Furthermore, VAPs might be at the origin of the difficulties of H passivation at the Ge/GeO2 interface. Since threefold Ge atoms are negatively charged and threefold O atoms are positively charged, VAPs give rise to dipoles. These dipoles may reduce the interface dipole created by the electronegativity difference in the Ge-3O bond. With this mechanism, we can explain the wide range of experimental valence band offsets (VBOs) with the occurrence of different density levels of VAPs at the Ge/GeO2 interface. This suggestion is further confirmed by the determination of the VBO and Ge 3d core-level shift for an atomistic model structure of the Ge/GeO2 interface. Both values are systematically lower than typical experimental values for the Ge/GeO2 interface. Taking the extra dipole into account, our calculated VBOs and XPS shifts are in excellent agreement with experimental values. These results confirm that the structural properties of the Ge/GeO2 interface deviate significantly from its Si counterpart.

Extrinsic Defects in Amorphous Oxides: Hydrogen, Carbon, and Nitrogen Impurities in Alumina

Francesco Ambrosio, Zhendong Guo, Alfredo Pasquarello

We present a procedure for addressing extrinsic defects in amorphous oxides, in which the most stable defect configurations are identified through ab initio molecular dynamics in various charge states and studied through hybrid functional calculations. The protocol is further complemented with an electron counting scheme based on maximally localized Wannier functions, which allows one to identify the nominal charge state and the composition of the defect core unit. Here, we apply this approach to the study of hydrogen, carbon and nitrogen impurities in amorphous alumina (alpha-Al2O3), a highly relevant material for technological applications. Hydrogen is found to be amphoteric with a thermodynamic +1/-1 charge transition level lying at similar to 4.6 eV above the valence band maximum, in qualitative agreement with results obtained with crystalline models, but at a substantially different energy level. Hydroxyl groups are further shown to lead to the same defect states as observed for hydrogen. Application of our procedure to carbon and nitrogen impurities leads to structural configurations that are found to depend on the total charge set in the simulation cell. Through the adopted electron counting rule, we assess that carbon and nitrogen impurities are only found in neutral and in singly positive charge states, respectively. This indicates that neither carbon nor nitrogen give charge transition levels in the band gap, in strong contrast with results achieved for crystalline models. In addition, the defect core units are shown to incorporate a varying number of oxygen atoms, by which their formation energy depends on the oxygen chemical potential mu O. In oxygen-poor conditions, both the carbon and the nitrogen impurities favor bonding to Al atoms, while they tend to form single or double bonds with oxygen atoms as mu(0) increases. Based on the band alignment of alpha-Al2O3 with three technologically relevant semiconductors (GaAs, GaN and alpha-Fe2O3), we discuss the possible role of point defects in degrading the performance of electronic devices and in favoring hole transport across the oxide in water-splitting setups.

2019

Band offsets at Ge/GeO2 interfaces: Effect of different interfacial bonding patterns

Jan Felix Binder, Peter Broqvist, Alfredo Pasquarello

Using hybrid density functional calculations, we investigate possible origins for the large variation of band offsets measured at Ge/GeO2 interfaces. We consider atomistic model interfaces with both amorphous and crystalline oxides, in which the bond density reduction accounts for the mass densities of the two interface components. To the extent that all the Ge atoms are fourfold coordinated and all the O atoms are twofold coordinated, the band offsets are found to remain constant within 0.1 eV. We then investigate the role of valence alternation pairs consisting of negatively charged Ge dangling bonds and positively charged threefold coordinated O atoms, which have been suggested to occur in sizeable concentrations in substoichiometric germanium oxide. A valence alternation pair is introduced in one of the atomistic models and is found to affect the band alignment by contributing to the interface dipole. The calculated band offsets shift by 0.7 eV for an areal concentration of valence alternation pairs corresponding to one pair per 8 Ge interface atoms. These pairs would act as fixed charges and are not expected to directly contribute to the defect density in the germanium band gap. The occurrence of such bonding patterns offers a possible explanation for the large range of valence band offsets measured at this interface. (C) 2011 Elsevier B.V. All rights reserved.

Elsevier2011

Structural, Dynamical, and Electronic Properties of Liquid Water: A Hybrid Functional Study

Francesco Ambrosio, Giacomo Francesco Leonardo Miceli, Alfredo Pasquarello

We study structural, dynamical, and electronic properties of liquid water through ab initio molecular dynamics (MD) simulations based on a hybrid functional which includes nonlocal van der Waals (vdW) interactions. The water dimer, the water hexamer, and two phases of ice are studied as benchmark cases. The hydrogen-bond energy depends on the balance between Fock exchange and vdW interactions. Moreover, the energetic competition between extended and compact structural motifs is found to be well described by theory provided vdW interactions are accounted for. Applied to the hydrogen-bond network of liquid water, the dispersion interactions favor more compact structural motifs, bring the density closer to the experimental value, and improve the agreement with experimental observables such as radial distribution functions. The description of the self-diffusion coefficient is also found to improve upon the combined consideration of Fock exchange and vdW interactions. The band gap and the band edges are found to agree with experiment within 0.1 eV.

Amer Chemical Soc2016

Extrinsic Defects in Amorphous Oxides: Hydrogen, Carbon, and Nitrogen Impurities in Alumina

Francesco Ambrosio, Zhendong Guo, Alfredo Pasquarello

2019