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

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

We present a comprehensive and up-to-date compilation of band parameters for all of the nitrogen-containing III–V semiconductors that have been investigated to date. The two main classes are: (1) “conventional” nitrides (wurtzite and zinc-blende GaN, InN, and AlN, along with their alloys) and (2) “dilute” nitrides (zinc-blende ternaries and quaternaries in which a relatively small fraction of N is added to a host III–V material, e.g., GaAsN and GaInAsN). As in our more general review of III–V semiconductor band parameters [I. Vurgaftman et al., J. Appl. Phys. 89, 5815 (2001)], complete and consistent parameter sets are recommended on the basis of a thorough and critical review of the existing literature. We tabulate the direct and indirect energy gaps, spin-orbit and crystal-field splittings, alloy bowing parameters, electron and hole effective masses, deformation potentials, elastic constants, piezoelectric and spontaneous polarization coefficients, as well as heterostructure band offsets. Temperature an...

Band parameters for nitrogen-containing semiconductors

Recent progress in processing and properties of ZnO

Neutral-donor--bound-exciton transitions have been observed in ZnO. The isolated neutral donors are made up of defect pair complexes. The neutral-donor nature of these pair complexes was determined from magnetic-field measurements and from two-electron transitions. Excited states of the neutral-donor bound excitons were observed in the form of rotator states analogous to rotational states of the ${\mathrm{H}}_{2}$ molecule.

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Neutral-donor–bound-exciton complexes in ZnO crystals

High-quality, melt-grown ZnO crystals are reported. The reflection and emission spectra of the melt-grown samples are compared with the same spectra from high-quality, vapor-grown ZnO crystals. We isolate the reflection and emission spectra predominantly related to the intrinsic properties associated with the wurtzite structure of the crystals. The quality of the crystals is reflected in the spectral reproduction of the intrinsic properties of the crystals. Both the ground state and the n=2 state of the free excitons associated with the A, B, and C valence bands of the crystals are spectrally observed in reflection. Assuming a hydrogenic character for the free excitons, the binding energy of these excitons associated with all three valence bands was determined. For the intrinsic emission spectra, attention was focused on the A-band free excitons and related optical parameters. Both the reflection and emission spectra for the melt-grown material compared very closely with the same spectra observed from high-quality vapor-grown ZnO samples. The details of both the reflection and emission spectra verify the high-quality of the melt-grown material.

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High-Quality, Melt-Grown ZnO Single Crystals

The crystal structure of ZnO is wurtzite and the stacking sequence of atomic layers along the “c” axis is not symmetric. As a result, a ZnO crystal surface that is normal to the c axis exposes one of two distinct polar faces, with (0001) being considered the O face and (0001) the Zn face. Photoluminescence (PL) measurements on the two faces reveal a striking difference. Two transitions are observed in PL that are dominant from the O face and barely observed in PL from the Zn face. These lines are identified as phonon replicas of a particular D0,X transition using energy separations, excitation dependence, and time-resolved PL measurements. In addition, PL emission from free excitons is found to be more intense from the O face than from the Zn face.

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Photoluminescence measurements from the two polar faces of ZnO

An unusual photoluminescence line X has been observed in ZnO at an energy between that of the common donor-bound excitons (DBEs) and the free excitons (FEs). In the presence of a high carrier concentration, induced by a second below-band gap laser, the DBEs decrease in intensity, due to screening, and both the FEs and X increase. Thus, X has free-exciton, rather than bound-exciton, character. However, its electric-field vector lies in the plane perpendicular to the c axis, as is also found for the DBEs. The appearance of X is discussed in terms of the polariton picture.

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T. C. Collins

Papers

Neutral-donor–bound-exciton complexes in ZnO crystals

High-Quality, Melt-Grown ZnO Single Crystals

Photoluminescence measurements from the two polar faces of ZnO

Polariton and Free-Exciton-Like Photoluminescence in ZnO

Optical Properties of ZnO