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

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

Point defects and impurities strongly affect the physical properties of materials and have a decisive impact on their performance in applications. First-principles calculations have emerged as a powerful approach that complements experiments and can serve as a predictive tool in the identification and characterization of defects. The theoretical modeling of point defects in crystalline materials by means of electronic-structure calculations, with an emphasis on approaches based on density functional theory (DFT), is reviewed. A general thermodynamic formalism is laid down to investigate the physical properties of point defects independent of the materials class (semiconductors, insulators, and metals), indicating how the relevant thermodynamic quantities, such as formation energy, entropy, and excess volume, can be obtained from electronic structure calculations. Practical aspects such as the supercell approach and efficient strategies to extrapolate to the isolated-defect or dilute limit are discussed. Recent advances in tractable approximations to the exchange-correlation functional ($\mathrm{DFT}+U$, hybrid functionals) and approaches beyond DFT are highlighted. These advances have largely removed the long-standing uncertainty of defect formation energies in semiconductors and insulators due to the failure of standard DFT to reproduce band gaps. Two case studies illustrate how such calculations provide new insight into the physics and role of point defects in real materials.

First-principles calculations for point defects in solids

Gallium nitride (GaN) and its allied binaries InN and AIN as well as their ternary compounds have gained an unprecedented attention due to their wide-ranging applications encompassing green, blue, violet, and ultraviolet (UV) emitters and detectors (in photon ranges inaccessible by other semiconductors) and high-power amplifiers. However, even the best of the three binaries, GaN, contains many structural and point defects caused to a large extent by lattice and stacking mismatch with substrates. These defects notably affect the electrical and optical properties of the host material and can seriously degrade the performance and reliability of devices made based on these nitride semiconductors. Even though GaN broke the long-standing paradigm that high density of dislocations precludes acceptable device performance, point defects have taken the center stage as they exacerbate efforts to increase the efficiency of emitters, increase laser operation lifetime, and lead to anomalies in electronic devices. The p...

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Luminescence properties of defects in GaN

The role of extended and point defects, and key impurities such as C, O, and H, on the electrical and optical properties of GaN is reviewed. Recent progress in the development of high reliability contacts, thermal processing, dry and wet etching techniques, implantation doping and isolation, and gate insulator technology is detailed. Finally, the performance of GaN-based electronic and photonic devices such as field effect transistors, UV detectors, laser diodes, and light-emitting diodes is covered, along with the influence of process-induced or grown-in defects and impurities on the device physics.

Gan : processing, defects, and devices

Hydrogen interactions with imperfections in crystalline metals and semiconductors are reviewed. Emphasis is given to mechanistic experiments and theoretical advances contributing to predictive understanding. Important directions for future research are discussed.

Hydrogen interactions with defects in crystalline solids

List of Contributors. Preface. G. Davies, Optical Measurements of Point Defects. P.M. Mooney, Defect Identification Using Capacitance Spectroscopy. M. Stavola, Vibrational Spectroscopy of Light Element Impurities in Semiconductors. P. Schwander, W.D. Rau, C. Kisielowski, M. Gribelyuk, and A. Ourmazd, Defect Processes in Semiconductors Studied at the Atomic Level by Transmission Electron Microscopy. N.D. Jager and E.R. Weber, Scanning Tunneling Microscopy of Defects in Semiconductors. Subject Index. Contents of Volumes in This Series.

Identification of defects in semiconductors

We present data on oxygen diffusivity in silicon for the temperature range 270–400 °C. The diffusivity is determined from the recovery kinetics of a stress induced dichroism in the 9‐μm oxygen infrared absorption band. We combine our data for well dispersed oxygen (i.e., crystals heat treated at 1350 °C for 20 h), with Mikkelsen’s recent mass transport work at higher temperature to obtain the diffusivity, D=0.17 exp (−2.54/kT), for the range 330–1240 °C. We have also found that the oxygen atomic hopping times can be as much as 100 times faster in crystals that have not received the 1350 °C heat treatment.

Diffusivity of oxygen in silicon at the donor formation temperature

The annealing behavior of the free-carrier absorption, O-H vibrational absorption, and photoluminescence lines previously associated with H-related donors in ZnO has been studied. One set of H-related defects gives rise to O-H local vibrational mode absorption at either 3326 or $3611\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$, with the relative intensities of these lines depending on the source of the ZnO starting material. These O-H lines anneal away together at 150 \ifmmode^\circ\else\textdegree\fi{}C along with $\ensuremath{\sim}80%$ of the free carriers introduced by H. The common annealing behavior of the O-H ir lines suggests that they are closely related. An additional defect produced by hydrogenation is thermally stable up to an annealing temperature of 500 \ifmmode^\circ\else\textdegree\fi{}C where a bound-exciton photoluminescence line often associated with H in ZnO is also annealed away. This more thermally stable donor accounts for $\ensuremath{\sim}20%$ of the free carriers introduced by H. These experiments on H in ZnO reveal a complex behavior with several defects being introduced and with properties that depend strongly on the source of the ZnO starting material.

Hydrogen local modes and shallow donors in ZnO

Several new infrared absorption bands have been discovered in hydrogen passivated silicon doped with P, As, and Sb. The frequency shift upon substitution of D for H confirms the assignment of these bands to donor-H complexes. Thermal annealing experiments, in which both the absorption due to complexes and to free carriers were measured, confirm that donor passivation is due to complex formation, and yield the stability of the complexes. Our results suggest that H is bonded to Si rather than the donor directly.

Michael Stavola

Papers

Hydrogen interactions with defects in crystalline solids

Identification of defects in semiconductors

Diffusivity of oxygen in silicon at the donor formation temperature

Hydrogen local modes and shallow donors in ZnO

Donor-hydrogen complexes in passivated silicon.