Zinc oxide (ZnO) is a wide band gap semiconductor material with attractive features for light emitting devices, photovoltaics, chemical sensors and spintronics. In the past 10 yr ZnO has attracted tremendous interest from the materials science and semiconductor physics research communities, and in this review recent progress in (i) bulk growth, (ii) understanding of the role of hydrogen and (iii) formation of high-quality Schottky barrier (SB) diodes, are discussed for single crystalline ZnO. In (i), the emphasis is put on hydrothermally grown material and how the concentration of intentional and unintentional impurities, such as In and Li, can be controlled and modified by high temperature treatment and defect engineering involving vacancy clusters. In (ii), different possible configurations of hydrogen as a shallow donor are evaluated based on results from calculations employing the density-functional-theory as well as from experimental studies of local vibrational modes using Fourier transform infrared spectroscopy. Further, hydrogen is demonstrated to be very reactive and the interaction with zinc vacancies, group I and group V elements, and transition metals are elucidated. Moreover, the diffusion of hydrogen is found to be rapid and limited by the concentration of traps in hydrothermal samples, and it is argued that isolated (free) hydrogen is not very likely to exist in ZnO at room temperature. In (iii), a compilation of the literature data illustrates that the SB heights for metals deposited on n-type samples have no correlation with the metal work function, violating the fundamental Schottky–Mott model. The role of surface preparation cannot be overestimated and in several cases an oxidation of the surface prior to metal deposition is shown to be beneficial for the formation of high barrier SB diodes. The effects of near-surface defects, such as oxygen vacancies, and contact inhomogeneity are also addressed. However, in spite of the significant progress made in the past 5–7 years, a thorough understanding of the SB formation to ZnO is still lacking. Finally, results from characterization of electrically active point defects employing the SB contacts and junction spectroscopic techniques are reviewed and the identification of some prominent bandgap states is critically evaluated.

A combination of depth-resolved electronic and structural techniques reveals that native point defects can play a major role in ZnO Schottky barrier formation and charged carrier doping. Previous work ignored these lattice defects at metal-ZnO interfaces due to relatively low point defect densities in the bulk. At higher densities, however, they may account for the wide range of Schottky barrier results in the literature. Similarly, efforts to control doping type and density usually treat native defects as passive, compensating donors or acceptors. Recent advances provide a deeper understanding of the interplay between native point defects and electronic properties at ZnO surfaces, interfaces, and epitaxial films. Key to ZnO Schottky barrier formation is a massive redistribution of native point defects near its surfaces and interfaces. It is now possible to measure the energies, densities, and in many cases the type of point defects below the semiconductor-free surface and its metal interface with nanoscale precision. Depth-resolved cathodoluminescence spectroscopy of deep level emissions calibrated with electrical techniques show that native point defects can (1) increase by orders of magnitude in densities within tens of nanometers of the semiconductor surface, (2) alter free carrier concentrations and band profiles within the surface space charge region, (3) dominate Schottky barrier formation for metal contacts to ZnO, and (4) play an active role in semiconductor doping. The authors address these issues by clearly identifying transition energies of leading native point defects and defect complexes in ZnO and the effects of different annealing methods on their spatial distributions on a nanoscale. These results reveal the interplay between ZnO electronic defects, dopants, polarity, and surface nanostructure, highlighting new ways to control ZnO Schottky barriers and doping.

No abstract