The semiconductor ZnO has gained substantial interest in the research community in part because of its large exciton binding energy (60meV) which could lead to lasing action based on exciton recombination even above room temperature. Even though research focusing on ZnO goes back many decades, the renewed interest is fueled by availability of high-quality substrates and reports of p-type conduction and ferromagnetic behavior when doped with transitions metals, both of which remain controversial. It is this renewed interest in ZnO which forms the basis of this review. As mentioned already, ZnO is not new to the semiconductor field, with studies of its lattice parameter dating back to 1935 by Bunn [Proc. Phys. Soc. London 47, 836 (1935)], studies of its vibrational properties with Raman scattering in 1966 by Damen et al. [Phys. Rev. 142, 570 (1966)], detailed optical studies in 1954 by Mollwo [Z. Angew. Phys. 6, 257 (1954)], and its growth by chemical-vapor transport in 1970 by Galli and Coker [Appl. Phys. ...

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A comprehensive review of zno materials and devices

In the past ten years we have witnessed a revival of, and subsequent rapid expansion in, the research on zinc oxide (ZnO) as a semiconductor. Being initially considered as a substrate for GaN and related alloys, the availability of high-quality large bulk single crystals, the strong luminescence demonstrated in optically pumped lasers and the prospects of gaining control over its electrical conductivity have led a large number of groups to turn their research for electronic and photonic devices to ZnO in its own right. The high electron mobility, high thermal conductivity, wide and direct band gap and large exciton binding energy make ZnO suitable for a wide range of devices, including transparent thin-film transistors, photodetectors, light-emitting diodes and laser diodes that operate in the blue and ultraviolet region of the spectrum. In spite of the recent rapid developments, controlling the electrical conductivity of ZnO has remained a major challenge. While a number of research groups have reported achieving p-type ZnO, there are still problems concerning the reproducibility of the results and the stability of the p-type conductivity. Even the cause of the commonly observed unintentional n-type conductivity in as-grown ZnO is still under debate. One approach to address these issues consists of growing high-quality single crystalline bulk and thin films in which the concentrations of impurities and intrinsic defects are controlled. In this review we discuss the status of ZnO as a semiconductor. We first discuss the growth of bulk and epitaxial films, growth conditions and their influence on the incorporation of native defects and impurities. We then present the theory of doping and native defects in ZnO based on density-functional calculations, discussing the stability and electronic structure of native point defects and impurities and their influence on the electrical conductivity and optical properties of ZnO. We pay special attention to the possible causes of the unintentional n-type conductivity, emphasize the role of impurities, critically review the current status of p-type doping and address possible routes to controlling the electrical conductivity in ZnO. Finally, we discuss band-gap engineering using MgZnO and CdZnO alloys.

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Fundamentals of zinc oxide as a semiconductor

Over the past decade the theoretical description of surface reactions has undergone a radical development. Advances in density functional theory mean it is now possible to describe catalytic reactions at surfaces with the detail and accuracy required for computational results to compare favourably with experiments. Theoretical methods can be used to describe surface chemical reactions in detail and to understand variations in catalytic activity from one catalyst to another. Here, we review the first steps towards using computational methods to design new catalysts. Examples include screening for catalysts with increased activity and catalysts with improved selectivity. We discuss how, in the future, such methods may be used to engineer the electronic structure of the active surface by changing its composition and structure.

Towards the computational design of solid catalysts

We have performed a comprehensive first-principles investigation of native point defects in ZnO based on density functional theory within the local density approximation (LDA) as well as the $\mathrm{LDA}+U$ approach for overcoming the band-gap problem. Oxygen deficiency, manifested in the form of oxygen vacancies and zinc interstitials, has long been invoked as the source of the commonly observed unintentional $n$-type conductivity in ZnO. However, contrary to the conventional wisdom, we find that native point defects are very unlikely to be the cause of unintentional $n$-type conductivity. Oxygen vacancies, which have most often been cited as the cause of unintentional doping, are deep rather than shallow donors and have high formation energies in $n$-type ZnO (and are therefore unlikely to form). Zinc interstitials are shallow donors, but they also have high formation energies in $n$-type ZnO and are fast diffusers with migration barriers as low as $0.57\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$; they are therefore unlikely to be stable. Zinc antisites are also shallow donors but their high formation energies (even in Zn-rich conditions) render them unlikely to be stable under equilibrium conditions. We have, however, identified a different low-energy atomic configuration for zinc antisites that may play a role under nonequilibrium conditions such as irradiation. Zinc vacancies are deep acceptors and probably related to the frequently observed green luminescence; they act as compensating centers in $n$-type ZnO. Oxygen interstitials have high formation energies; they can occur as electrically neutral split interstitials in semi-insulating and $p$-type materials or as deep acceptors at octahedral interstitial sites in $n$-type ZnO. Oxygen antisites have very high formation energies and are unlikely to exist in measurable concentrations under equilibrium conditions. Based on our results for migration energy barriers, we calculate activation energies for self-diffusion and estimate defect-annealing temperatures. Our results provide a guide to more refined experimental studies of point defects in ZnO and their influence on the control of $p$-type doping.

Native point defects in ZnO

Dilute ferromagnetic oxides having Curie temperatures far in excess of 300 K and exceptionally large ordered moments per transition-metal cation challenge our understanding of magnetism in solids. These materials are high-k dielectrics with degenerate or thermally activated n-type semiconductivity. Conventional super-exchange or double-exchange interactions cannot produce long-range magnetic order at concentrations of magnetic cations of a few percent. We propose that ferromagnetic exchange here, and in dilute ferromagnetic nitrides, is mediated by shallow donor electrons that form bound magnetic polarons, which overlap to create a spin-split impurity band. The Curie temperature in the mean-field approximation varies as (xdelta)(1/2) where x and delta are the concentrations of magnetic cations and donors, respectively. High Curie temperatures arise only when empty minority-spin or majority-spin d states lie at the Fermi level in the impurity band. The magnetic phase diagram includes regions of semiconducting and metallic ferromagnetism, cluster paramagnetism, spin glass and canted antiferromagnetism.

Donor impurity band exchange in dilute ferromagnetic oxides.

The characterization of native point defects in ZnO is still a question of debate. For example, experimental evidence for ZnO with an excess of Zn is inconclusive as to whether the dominant defects are metal interstitials or oxygen vacancies. This information is essential to understand the behavior of the material and to tailor its numerous technological applications. We use the first-principles pseudopotential method to determine the electronic structure, atomic geometry, and formation energy of native point defects in ZnO. Interstitials, vacancies, and antisites in their relevant charge states are considered and the effects of dopants are also discussed. The results show that both the Zn and O vacancies are the relevant defects in ZnO. We also propose a possible transition mechanism and defect center responsible for the experimentally observed green luminescence.

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First-principles study of native point defects in ZnO

A study of the average voltage to intercalate lithium in various metal oxides is presented. By combining the ab initio pseudopotential method with basic thermodynamics the average intercalation voltage can be predicted without the need for experimental data. This procedure is used to systematically study the effect of metal chemistry, anion chemistry, and structure. It is found that Li is fully ionized in the intercalated compounds with its charge transferred to the anion and to the metal. The substantial charge transfer to the anion is responsible for the large voltage difference between oxides, sulfides, and selenides. Ionic relaxation, as a result of Li intercalation, causes nonrigid-band effects in the density of states of these materials. Suggestions for compounds that may have a substantially larger voltage than currently used materials are also presented. @S0163-1829~97!01028-X#

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Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides

Ab initio calculation of the intercalation voltage of lithium-transition-metal oxide electrodes for rechargeable batteries

Application of first-principles calculations to the design of rechargeable Li-batteries

The CaO–MgO system is used as a prototype system to evaluate the accuracy of several energy and entropy approximations for predicting solid-state phase diagrams in ionic materials. Configurational disorder between the cations is parameterized with the cluster expansion technique. The vibrational contribution to the free energy is incorporated with a harmonic model that accounts for the dependence of the vibrational density of states on the cation configuration. The CaO–MgO phase diagram can be predicted very accurately with quantum mechanical energy methods, without the use of any adjustable parameters. Published empirical potential parameters for the CaO–MgO system reproduce the qualitative features of the phase diagram but significantly underestimate the solubility limits. Parameters that reasonably reproduce the quantum mechanical results are presented.

A Model to Compute Phase Diagrams in Oxides with Empirical or First‐Principles Energy Methods and Application to the Solubility Limits in the CaO–MgO System

A. F. Kohan

Papers

First-principles study of native point defects in ZnO

Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides

Ab initio calculation of the intercalation voltage of lithium-transition-metal oxide electrodes for rechargeable batteries

Application of first-principles calculations to the design of rechargeable Li-batteries

A Model to Compute Phase Diagrams in Oxides with Empirical or First‐Principles Energy Methods and Application to the Solubility Limits in the CaO–MgO System