Hydrogen adsorption on the ZnO $(1\bar{1}00)$ surface: ab initio hybrid density functional linear combination of atomic orbitals calculations

Abstract

Hydrogen atoms unavoidably presented in ZnO samples or thin films during their synthesis considerably affect electrical conductivity. Results of first principles hybrid functional linear combination of atomic orbitals calculations are discussed for hydrogen atoms incorporated in bulk or adsorbed upon non-polar ZnO surfaces. The energy of H incorporation, atomic relaxation, electronic density redistribution and modification of the electronic structure are compared for both surface adsorption and bulk absorption. It is shown that hydrogen forms a strong bonding with the surface O ions (Eads = 2.7 eV) whereas its incorporation into bulk is energetically quite unfavorable. Hydrogen adsorption reduces the surface energy. Surface hydrogen atoms are very shallow donors, thus contributing to the electronic conductivity and ZnO metallization.

Doped ZnO 1D Nanostructures: Synthesis, Properties, and Photodetector Application

“…The incorporation of dopants into a ZnO cluster has been calculated using the first principles method and density functional theory (DFT), which are useful to study doped ZnO clusters. Recently, some research groups have investigated the physical properties of various dopants on (ZnO) n ( n = integer) clusters, as shown in Figure . The effects of relaxation and electronic confinement can be studied with atomistic models.…”

“…(b) H element, Reproduced with permission. [ 71 ] Copyright 2014, IOP. (c) P element, Reproduced with permission.…”

Thermodynamics of Hydrogen Adsorption and Incorporation at the ZnO(101̅0) Surface

“…The two hydrogen adsorption configurations previously mentioned (1 ML-O and 2 ML-both) have also been considered by theoretical works using a variety of methods. − Zapol used Hartree–Fock calculations to study hydrogen adsorption in both configurations, finding adsorption on both sides of the dimer (2 ML-both) to have a more favorable adsorption energy per atom than adsorption only on the O side (1 ML-O). Wander and Harisson used B3LYP hybrid functional calculations to study the geometry and electronic structure of (only) the heterolytically terminated 2 ML-both configuration.…”

“…Most recently, Usseinov et al 20 used hybrid PBE0 calculations to study hydrogen adsorbed on both sides of the dimer and on the O side at several different coverages. An important discrepancy is found between the Zapol and Usseinov results, with Zapol predicting a larger adsorption energy per atom for the 2 ML-both configuration and Usseinov et al predicting the opposite.…”

The electrical conductivity of zinc oxide crystals. First principles study

“…В работе использован гибридный обменно-корреляционный функционал PBE0. Как было показано ранее, этот функционал обеспечивает надежное описание геометрической, электронной структуры и энергетики дефектов в широком спектре материалов [25,26]. В частности, гибридные функционалы, такие как PBE0, обеспечивают гораздо лучшее предсказание запрещенной зоны полупроводников, чем приближение локальной плотности (LDA)или приближение обобщенных градиентов (GGA).…”