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

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

Wurtzitic ZnO is a wide-bandgap (3.437 eV at 2 K) semiconductor which has many applications, such as piezoelectric transducers, varistors, phosphors, and transparent conducting films. Most of these applications require only polycrystalline material; however, recent successes in producing large-area single crystals have opened up the possibility of producing blue and UV light emitters, and high-temperature, high-power transistors. The main advantages of ZnO as a light emitter are its large exciton binding energy (60 meV), and the existence of well-developed bulk and epitaxial growth processes; for electronic applications, its attractiveness lies in having high breakdown strength and high saturation velocity. Optical UV lasing, at both low and high temperatures, has already been demonstrated, although efficient electrical lasing must await the further development of good, p-type material. ZnO is also much more resistant to radiation damage than are other common semiconductor materials, such as Si, GaAs, CdS, and even GaN; thus, it should be useful for space applications.

Recent Advances in ZnO Materials and Devices

First-principles calculations have evolved from mere aids in explaining and supporting experiments to powerful tools for predicting new materials and their properties. In the first part of this review we describe the state-of-the-art computational methodology for calculating the structure and energetics of point defects and impurities in semiconductors. We will pay particular attention to computational aspects which are unique to defects or impurities, such as how to deal with charge states and how to describe and interpret transition levels. In the second part of the review we will illustrate these capabilities with examples for defects and impurities in nitride semiconductors. Point defects have traditionally been considered to play a major role in wide-band-gap semiconductors, and first-principles calculations have been particularly helpful in elucidating the issues. Specifically, calculations have shown that the unintentional n-type conductivity that has often been observed in as-grown GaN cannot be a...

First-principles calculations for defects and impurities: Applications to III-nitrides

High-energy electron irradiation in ZnO produces shallow donors at about ${E}_{C}\ensuremath{-}30\mathrm{meV}$. Because the production rate is much higher for Zn-face (0001) than O-face $(000\overline{1})$ irradiation, the donor is identified as a Zn-sublattice defect, most likely the interstitial ${\mathrm{Zn}}_{I}$ or a ${\mathrm{Zn}}_{I}$-related complex. The donor energy is quite close to that of the unirradiated sample, and of other samples discussed in the literature, strongly suggesting that ${\mathrm{Zn}}_{I}$ (and not ${V}_{\mathrm{O}}$) is the dominant native shallow donor in ZnO. An exceptionally high displacement threshold energy $(\ensuremath{\sim}1.6\mathrm{MeV})$ is quantitatively explained in terms of a multiple-displacement model.

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Residual Native Shallow Donor in ZnO

High-energy (0.7{endash}1MeV) electron irradiation in GaN grown on sapphire produces shallow donors and deep or shallow acceptors at equal rates, 1{plus_minus}0.2 cm{sup {minus}1}. The data, in conjunction with theory, are consistent only with the shallow donor being the N vacancy, and the acceptor the N interstitial. The N-vacancy donor energy is 64{plus_minus}10 meV, much larger than the value of 18meV found for the residual donor (probably Si) in this material. The Hall-effect measurements also reveal a degenerate n -type layer at the GaN/sapphire interface which must be accounted for to get the proper donor activation energy. {copyright} {ital 1997} {ital The American Physical Society}

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Defect Donor and Acceptor in GaN

High-energy (>1.6 MeV) electrons create acceptors and donors in single-crystal ZnO. Greater damage is observed for irradiation in the [0001] direction (Zn face) than in the [0001] direction (O face). The major annealing stage occurs at about 300–325 °C, and is much sharper for defects produced by Zn-face irradiation, than for those resulting from O-face irradiation. The defects appear to have a chain character, rather than being simple, near-neighbor vacancy/interstitial Frenkel pairs. These experiments suggest that ZnO is significantly more “radiation hard” than Si, GaAs, or GaN, and should be useful for applications in high-irradiation environments, such as electronics in space satellites.

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Production and annealing of electron irradiation damage in ZnO

Deep-level transient spectroscopy measurements of n-type GaN epitaxial layers irradiated with 1-MeV electrons reveal an irradiation-induced electron trap at EC−0.18 eV. The production rate is approximately 0.2 cm−1, lower than the rate of 1 cm−1 found for the N vacancy by Hall-effect studies. The defect trap cannot be firmly identified at this time.

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Electron-Irradiation-Induced Deep Level in n -Type GaN

1 MeV electron irradiation has been performed in degenerate, n‐type (n≂2×1017 cm−3), molecular beam epitaxial GaAs layers, and Hall effect measurements have been carried out during the irradiation in order to get accurate defect production data. The results have been fitted with statistical models, and are most consistent with the usual E1 (EC−0.045 eV) and E2 (EC−0.15 eV) levels being the (−/0) and (0/+) transitions of the As vacancy, respectively. Also, an acceptor well below EC−0.15 eV is produced at a much higher rate than that of E1 and E2.

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Joseph W. Hemsky

Papers

Residual Native Shallow Donor in ZnO

Defect Donor and Acceptor in GaN

Production and annealing of electron irradiation damage in ZnO

Electron-Irradiation-Induced Deep Level in n -Type GaN

Defect Models in Electron-Irradiated N-Type GaAs