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

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

High concentrations of defects are introduced into nanoscale ZnO through non-equilibrium processes and resultant blue emissions are comprehensively analyzed, focusing on defect origins and broad controls. Some ZnO nanoparticles exhibit very strong blue emissions, the intensity of which first increase and then decrease with annealing. These visible emissions exhibit strong and interesting excitation dependences: 1) the optimal excitation energy for blue emissions is near the bandgap energy, but the effective excitation can obviously be lower, even 420 nm (2.95 eV < Eg = 3.26 eV); in contrast, green emissions can be excited only by energies larger than the bandgap energy; and, 2) there are several fixed emitting wavelengths at 415, 440, 455 and 488 nm in the blue wave band, which exhibit considerable stability in different excitation and annealing conditions. Mechanisms for blue emissions from ZnO are proposed with interstitial-zinc-related defect levels as initial states. EPR spectra reveal the predominance of interstitial zinc in as-prepared samples, and the evolutions of coexisting interstitial zinc and oxygen vacancies with annealing. Furthermore, good controllability of visible emissions is achieved, including the co-emission of blue and green emissions and peak adjustment from blue to yellow.

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Blue Luminescence of ZnO Nanoparticles Based on Non‐Equilibrium Processes: Defect Origins and Emission Controls

We present our investigations on the absorption and emission properties of the neutral oxygen vacancy in ZnO. Temperature-dependent photoluminescence (PL) experiments allow to determine the zero-phonon-energy of the emission and its phonon-coupling parameters. The absorption to the singlet excited state is observed in PL-excitation experiments at energies above 3.1 eV. Relaxation drives the system from the singlet, diamagnetic, excited state to the emissive, paramagnetic triplet state. Applying the Mollwo–Ivey relation for the energetical position of the F-centre absorption as a function of the anion–cation distance, we find that the oxygen vacancies in ZnO fit perfectly in the line given by MgO, CaO, SrO and BaO.

Oxygen vacancies in ZnO

The 1.8 eV luminescence band in GaN grown by molecular beam epitaxy is studied by photo-luminescence (PL) and magnetic resonance. Optically detected magnetic resonance (ODMR) shows that deep centres with g = 1.98 and g = 2.01 are involved in the recombination. The results of the PL experiments indicate that the 1.8 eV recombination can be further fed by shallow centres like shallow donors or excitons.

The Red (1.8 eV) Luminescence in Epitaxially Grown GaN

In order to investigate the defects responsible for the sub-band-gap absorption in ZnGeP2 optically detected magnetic resonance (ODMR) using the magnetic circular dichroism of the absorption (MCDA) as detection channel was applied. This is the first ODMR study of defects in II–IV–V2 chalcopyrites. The experiments exhibit that three different native defects contribute to the absorption in the spectral range from 0.5 eV to the band-gap energy of about 2.0 eV. The Ge antisite defects show a dominant transition near the band edge. Zn vacancies show strong MCD above 1.6 eV and below 1 eV, and the P vacancies are detected over the complete spectral range. In combination with photoinduced EPR studies these results reveal the contributions of the different defects to the broad absorption band. Peculiarities in the MCD of the Zn-vacancies are explained in terms of long spin–lattice relaxation times.

N.G. Romanov

Papers

Oxygen vacancies in ZnO

The Red (1.8 eV) Luminescence in Epitaxially Grown GaN

Optically detected magnetic resonance experiments on native defects in ZnGeP2