On the Structure of Oxygen Deficient Amorphous Oxide Films.

Understanding defects in amorphous oxide films and heterostructures is vital to improving performance of microelectronic devices, thin-film transistors, and electrocatalysis. However, to what extent the structure and properties of point defects in amorphous solids are similar to those in the crystalline phase are still debated. The validity of this analogy and the experimental and theoretical evidence of the effects of oxygen deficiency in amorphous oxide films are critically discussed. The authors start with the meaning and significance of defect models, such as "oxygen vacancy" in crystalline oxides, and then introduce experimental and computational methods used to study intrinsic defects in amorphous oxides and discuss their limitations and challenges. To test the validity of existing defect models, ab initio molecular dynamics is used with a non-local density functional to model the structure and electronic properties of oxygen-deficient amorphous alumina. Unlike some previous studies, the formation of deep defect states in the bandgap caused by the oxygen deficiency is found. Apart from atomistic structures analogous to crystal vacancies, the formation of more stable defect states characterized by the bond formation between under-coordinated Al ions is shown. The limitations of such defect models and how they may be overcome in simulations are discussed.

Properties of intrinsic point defects and dimers in hexagonal boron nitride.

Hexagonal boron nitride (hBN) is a wide gap 2D layered material with good insulating properties. Intrinsic point defects in hBN play an important role in its applications as a dielectric in 2D electronic devices. However, the electronic properties of these defects are still poorly understood. We have calculated the structure and properties of a wide range of intrinsic point defects in the bulk of hBN using hybrid density functional theory (DFT). These include vacancies and interstitial states of B and N as well as di- and tri-vacancies. For each isolated defect, multiple charge states are calculated, and for each charge state multiple spin states are investigated. Positions of defect charge transition levels in the band gap of hBN are calculated. In particular, we predict that B vacancies are likely to be negatively charged in contact with graphene and other metals. Calculations of the interaction between vacancies predict that divacancies in both B and N sublattices are strongly binding. Moreover, the interaction of single B and N vacancies in adjacent layers induces the creation of -N-N- and -B-B- molecular bridges, which greatly distort the local structure, leading to local bond weakening. These results provide further insight into the properties of defects which can be responsible for degradation of hBN based devices.

First principles calculations of optical properties for oxygen vacancies in binary metal oxides.

Using an advanced computational methodology implemented in CP2K, a non-local PBE0-TC-LRC density functional and the recently implemented linear response formulation of the Time-dependent Density Functional Theory equations, we test the interpretation of the optical absorption and photoluminescence signatures attributed by previous experimental and theoretical studies to O-vacancies in two widely used oxides-cubic MgO and monoclinic (m)-HfO2. The results obtained in large periodic cells including up to 1000 atoms emphasize the importance of accurate predictions of defect-induced lattice distortions. They confirm that optical transitions of O-vacancies in 0, +1, and +2 charge states in MgO all have energies close to 5 eV. We test the models of photoluminescence of O-vacancies proposed in the literature. The photoluminescence of VO +2 centers in m-HfO2 is predicted to peak at 3.7 eV and originate from radiative tunneling transition between a VO +1 center and a self-trapped hole created by the 5.2 eV excitation.

Intrinsic charge trapping in amorphous oxide films: status and challenges.

We review the current understanding of intrinsic electron and hole trapping in insulating amorphous oxide films on semiconductor and metal substrates. The experimental and theoretical evidences are provided for the existence of intrinsic deep electron and hole trap states stemming from the disorder of amorphous metal oxide networks. We start from presenting the results for amorphous (a) HfO2, chosen due to the availability of highest purity amorphous films, which is vital for studying their intrinsic electronic properties. Exhaustive photo-depopulation spectroscopy measurements and theoretical calculations using density functional theory shed light on the atomic nature of electronic gap states responsible for deep electron trapping observed in a-HfO2. We review theoretical methods used for creating models of amorphous structures and electronic structure calculations of amorphous oxides and outline some of the challenges in modeling defects in amorphous materials. We then discuss theoretical models of electron polarons and bi-polarons in a-HfO2 and demonstrate that these intrinsic states originate from low-coordinated ions and elongated metal-oxygen bonds in the amorphous oxide network. Similarly, holes can be captured at under-coordinated O sites. We then discuss electron and hole trapping in other amorphous oxides, such as a-SiO2, a-Al2O3, a-TiO2. We propose that the presence of low-coordinated ions in amorphous oxides with electron states of significant p and d character near the conduction band minimum can lead to electron trapping and that deep hole trapping should be common to all amorphous oxides. Finally, we demonstrate that bi-electron trapping in a-HfO2 and a-SiO2 weakens Hf(Si)-O bonds and significantly reduces barriers for forming Frenkel defects, neutral O vacancies and O2- ions in these materials. These results should be useful for better understanding of electronic properties and structural evolution of thin amorphous films under carrier injection conditions.

Intrinsic electron trapping in amorphous oxide.

We demonstrate that electron trapping at intrinsic precursor sites is endemic in non-glass-forming amorphous oxide films. The energy distributions of trapped electron states in ultra-pure prototype amorphous (a)-HfO2 insulator obtained from exhaustive photo-depopulation experiments demonstrate electron states in the energy range of 2-3 eV below the oxide conduction band. These energy distributions are compared to the results of density functional calculations of a-HfO2 models of realistic density. The experimental results can be explained by the presence of intrinsic charge trapping sites formed by under-coordinated Hf cations and elongated Hf-O bonds in a-HfO2. These charge trapping states can capture up to two electrons, forming polarons and bi-polarons. The corresponding trapping sites are different from the dangling-bond type defects responsible for trapping in glass-forming oxides, such as SiO2, in that the traps are formed without bonds being broken. Furthermore, introduction of hydrogen causes formation of somewhat energetically deeper electron traps when a proton is immobilized next to the trapped electron bi-polaron. The proposed novel mechanism of intrinsic charge trapping in a-HfO2 represents a new paradigm for charge trapping in a broad class of non-glass-forming amorphous insulators.