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 review the physical properties of diluted magnetic semiconductors (DMS) of the type AII1−xMnxBVI (e.g., Cd1−xMnxSe, Hg1−xMnxTe). Crystallographic properties are discussed first, with emphasis on the common structural features which these materials have as a result of tetrahedral bonding. We then describe the band structure of the AII1−xMnxBVI alloys in the absence of an external magnetic field, stressing the close relationship of the sp electron bands in these materials to the band structure of the nonmagnetic AIIBVI ‘‘parent’’ semiconductors. In addition, the characteristics of the narrow (nearly localized) band arising from the half‐filled Mn 3d5 shells are described, along with their profound effect on the optical properties of DMS. We then describe our present understanding of the magnetic properties of the AII1−xMnxBVI alloys. In particular, we discuss the mechanism of the Mn++‐Mn++ exchange, which underlies the magnetism of these materials; we present an analytic formulation for the magnetic susc...

Diluted magnetic semiconductors

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

In this chapter, we will restrict our attention to the ferrites and a few other closely related materials. The great interest in ferrites stems from their unique combination of a spontaneous magnetization and a high electrical resistivity. The observed magnetization results from the difference in the magnetizations of two non-equivalent sub-lattices of the magnetic ions in the crystal structure. Materials of this type should strictly be designated as “ferrimagnetic” and in some respects are more closely related to anti-ferromagnetic substances than they are to ferromagnetics in which the magnetization results from the parallel alignment of all the magnetic moments present. We shall not adhere to this special nomenclature except to emphasize effects, which are due to the existence of the sub-lattices.

Ferromagnetic materials

LiB 3 O 5 (LBO) crystals are used to generate the second, third, and fourth harmonics of near-infrared solid-state lasers. At high power levels, the material’s performance is adversely affected by nonlinear absorption. We show that as-grown crystals contain oxygen and lithium vacancies. Transient absorption bands are formed when these intrinsic defects serve as traps for “free” electrons and holes created by x rays or by three- and four-photon absorption processes. Trapped electrons introduce a band near 300 nm and trapped holes produce bands in the 500-600 nm region. Electron paramagnetic resonance (EPR) is used to identify and characterize the electrons trapped at oxygen vacancies (the unpaired electron is localized on one neighboring boron). Self-trapped holes and lithium vacancies with the hole trapped on an adjacent oxygen are also observed with EPR. At room temperature, we predict that most of the unwanted defect-related ultraviolet absorption created by a short laser pulse will decay with a half-life of 29 µs. 

Oxygen vacancies in LiB₃O₅ crystals and their role in nonlinear absorption

Cadmium silicon phosphide, CdSiP2 (CSP), exhibits the highest d-coefficient (d36 = 85 pm/V) among all practical nonlinear optical crystals. Its large band gap of 2.45 eV allows for 1-micron pumping with widely-available Nd- and Yb-based laser sources, and its dispersion properties are such that a 1-um pump yields non-critically phase-matched temperature-tunable output between 6.2-6.5 um (an attractive range for minimally-invasive laser surgery). However, residual 1-um absorption losses in CSP are not insignificant (0.16-0.2 cm-1). In this work we focused on identifying, and ultimately minimizing, the point defects responsible for these losses by correlating EPR spectra with polarized absorption near 1-um. 

Minimizing 1-micron absorption losses in CdSiP2

High quality Ga-polarity GaN films were grown by plasma-assisted molecular beam epitaxy to study strain effects due to oxygen incorporation. Oxygen concentrations up to 2 × 1022 cm−3 were studied. Layers containing oxygen at levels above 1022 cm−3 exhibit severe cracking while oxygen concentrations less than 1021 cm−3 apparently does not introduce significant strain. Raman spectra of O2-doped films were evaluated with respect to spectra of unintentionally doped GaN films (n=4×1014 cm−3) grown under the same conditions except for the O2-flux. Analysis of the E2 (high frequency phonon mode near 570 cm−1) Raman band indicated the heaviest doped samples exhibit compressive strain. Frequency-shifts between 0.7 and 0.9 cm−1 were observed as a function of the distance from the crack edges in the heavily doped samples, implying a strain (δα/α) of the order of 5×10−4.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S1946427400644019

Raman Studies on Oxygen Doped GaN Grown by Molecular Beam Epitaxy

The angular dependence of terahertz (THz) emission from birefringent crystals can differ significantly from that of cubic crystals. Here we consider optical rectification in uniaxial birefringent materials, such as chalcopyrite crystals. The analysis is verified in (110)-cut ZnGeP_2 and compared to (zincblende) GaP. Although the crystals share the same nonzero second-order tensor elements, the birefringence in chalcopyrite crystals cause the pump pulse polarization to evolve as it propagates through the crystal, resulting in a drastically different angular dependence in chalcopyrite crystals. The analysis is extended to {012}- and {114}-cut chalcopyrite crystals and predicts more efficient conversion for the {114} crystal cut over the {012}- and {110}-cuts.

Terahertz generation by optical rectification in uniaxial birefringent crystals

The introduction of phosphorus and arsenic dopants into bulk Cd1−xMnx Te crystals grown by the Bridgman-Stockbarger technique has been studieA-with respect to the resulting optical properties. Samples with a Mn composition in the range 0.10 < x < 0.30, both as-grown and annealed, were investigated. A combination of room temperature transmittance and reflectance measurements over the spectral range from the ultraviolet to the far infrared has been used to gain information concerning the structural quality of the samples. Low temperature photoluminescence measurements (1.6−5 K) were used to determine optical quality and excitonic energies.

Nancy C. Giles

Papers

Oxygen vacancies in LiB₃O₅ crystals and their role in nonlinear absorption

Minimizing 1-micron absorption losses in CdSiP2

Raman Studies on Oxygen Doped GaN Grown by Molecular Beam Epitaxy

Terahertz generation by optical rectification in uniaxial birefringent crystals

Optical Properties of Doped Cd1−xMnxTe