First-Principles Approach for Energy Level Alignment at Aqueous Semiconductor Interfaces

Abstract

A first-principles approach is demonstrated to calculate the relationship between aqueous semiconductor interface structure and energy level alignment. The physical interface structure is sampled using density functional theory based molecular dynamics, yielding the interface electrostatic dipole. The $GW$ approach is used to place the electronic band edge energies of the semiconductor relative to the occupied $1b_1$ energy level in water. Application to the specific cases of non-polar $(10\bar{1}0)$ facets of GaN and ZnO reveals a significant role for the structural motifs at the interface, including the degree of interface water dissociation and the dynamical fluctuations in the interface Zn-O and O-H bond orientations. These effects contribute up to 0.5 eV.

Accepted in Phys. Rev. Lett. 5 pages, 4 figures, Supplemental Material: 3 pages, 4 figures

References in corpus (7)

• Van der Waals Density Functional for General Geometries
• Van der Waals density functionals applied to solids
• Density, structure and dynamics of water: the effect of Van der Waals interactions
• Band convergence and linearization error correction of all-electron GW calculations: The extreme case of zinc oxide
• Band Offsets at the Si/SiO${}_2$ Interface from Many-Body Perturbation Theory
• Solvent Induced Proton Hopping at a Water-Oxide Interface
• Ab initio studies of ionization potentials of hydrated hydroxide and hydronium

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• Quasiparticle electronic structure of phthalocyanine:TMD interfaces from first-principles $GW$
• Quantum-continuum calculation of the surface states and electrical response of silicon in solution
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• Voltage-dependent first-principles simulation of insertion of chloride ions into Al/Al${}_2$O${}_3$ interfaces using the Quantum Continuum Approximation
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