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

Since the successful demonstration of a blue light-emitting diode (LED)1, potential materials for making short-wavelength LEDs and diode lasers have been attracting increasing interest as the demands for display, illumination and information storage grow2,3,4. Zinc oxide has substantial advantages including large exciton binding energy, as demonstrated by efficient excitonic lasing on optical excitation5,6. Several groups have postulated the use of p-type ZnO doped with nitrogen, arsenic or phosphorus7,8,9,10, and even p–n junctions11,12,13. However, the choice of dopant and growth technique remains controversial and the reliability of p-type ZnO is still under debate14. If ZnO is ever to produce long-lasting and robust devices, the quality of epitaxial layers has to be improved as has been the protocol in other compound semiconductors15. Here we report high-quality undoped films with electron mobility exceeding that in the bulk. We have used a new technique to fabricate p-type ZnO reproducibly. Violet electroluminescence from homostructural p–i–n junctions is demonstrated at room-temperature.

Repeated temperature modulation epitaxy for p-type doping and light-emitting diode based on ZnO

We present a review of current research on the optical properties of ZnO nanostructures. We provide a brief introduction to different fabrication methods for various ZnO nanostructures and some general guidelines on how fabrication parameters (temperature, vapor-phase versus solution-phase deposition, etc.) affect their properties. A detailed discussion of photoluminescence, both in the UV region and in the visible spectral range, is provided. In addition, different gain (excitonic versus electron hole plasma) and feedback (random lasing versus individual nanostructures functioning as Fabry-Perot resonators) mechanisms for achieving stimulated emission are described. The factors affecting the achievement of stimulated emission are discussed, and the results of time-resolved studies of stimulated emission are summarized. Then, results of nonlinear optical studies, such as second-harmonic generation, are presented. Optical properties of doped ZnO nanostructures are also discussed, along with a concluding outlook for research into the optical properties of ZnO.

Optical properties of ZnO nanostructures.

An object is to provide a semiconductor device of which a manufacturing process is not complicated and by which cost can be suppressed, by forming a thin film transistor using an oxide semiconductor film typified by zinc oxide, and a manufacturing method thereof. For the semiconductor device, a gate electrode is formed over a substrate; a gate insulating film is formed covering the gate electrode; an oxide semiconductor film is formed over the gate insulating film; and a first conductive film and a second conductive film are formed over the oxide semiconductor film. The oxide semiconductor film has at least a crystallized region in a channel region.

Semiconductor device, and manufacturing method thereof

We describe the structural and optical properties of II–VI oxide alloys, MgxZn1−xO and CdyZn1−yO, grown by pulsed-laser deposition. Single-phase alloyed films of (Mg,Zn)O and (Cd,Zn)O with c-axis orientations were epitaxially grown on sapphire (0001) substrates. The maximum magnesium and cadmium concentrations (x=0.33 and y=0.07, respectively) were significantly larger than the thermodynamic solubility limits. The band gap energies systematically changed from 3.0 (y=0.07) to 4.0 eV (x=0.33) at room temperature. The photoluminescence peak energy deduced at 4.2 K could be tuned from 3.19 to 3.87 eV by using Cd0.07Zn0.93O and Mg0.33Zn0.67O at both ends, respectively. The lattice constants of the a axis were monotonically increasing functions of the concentrations of both alloys. The exciton–phonon coupling strength was determined in Cd0.01Zn0.99O grown on a lattice-matched ScAlMgO4 substrate.

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Band gap engineering based on MgxZn1−xO and CdyZn1−yO ternary alloy films

ZnO/Mg0.2Zn0.8O superlattices with a band-gap offset of about 0.5 eV were epitaxially grown by laser molecular-beam epitaxy on a sapphire(0001) substrate using a ZnO buffer layer. The superlattice structure with a period ranging from 8 to 18 nm was clearly verified by cross-sectional transmission electron microscopy, Auger depth profile, and x-ray diffraction. As the well layer thickness decreased below 5 nm, the photoluminescence peak and absorption edge in the photoluminescence excitation spectra showed a blueshift, indicating a quantum-size effect.

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Structure and optical properties of zno/mg0.2zn0.8o superlattices

Lattice-matched (Δa/a=0.09%) ScAlMgO4(0001) substrates were employed to grow single crystalline quality ZnO films by laser molecular-beam epitaxy. Extremely smooth surface represented by atomically flat terraces and half unit cell (0.26 nm) high steps and extremely small orientation fluctuations both in-plane (<0.02°) and out-of-plane (<0.01°) are achieved. The films have high mobility (∼100 cm2/V s) together with low residual carrier concentration (∼1015 cm−3). Excellent optical properties, including a clear doublet of A and B exciton peaks in absorption spectra, were also observed. These features could not be simultaneously achieved for ZnO films grown on sapphire(0001) having a large lattice mismatch (Δa/a=18%).

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Single crystalline ZnO films grown on lattice-matched ScAlMgO4(0001) substrates

Influences of point defects on the nonradiative processes in ZnO were studied using steady-state and time-resolved photoluminescence (PL) spectroscopy making a connection with the results of positron annihilation measurement. Free excitonic PL intensity naturally increased with the increase in the nonradiative PL lifetime (τnr). Density or size of Zn vacancies (VZn) decreased and τnr increased with increasing growth temperature in heteroepitaxial films grown on a ScAlMgO4 substrate. Use of homoepitaxial substrate further decreased the VZn density. However, τnr was the shortest for the homoepitaxial film; i.e., no clear dependence was found between τnr and density / size of VZn or positron scattering centers. The results indicated that nonradiative recombination processes are not solely governed by single point defects, but by certain defect species introduced by the presence of VZn such as vacancy complexes.

Correlation between the photoluminescence lifetime and defect density in bulk and epitaxial ZnO

The effect of confinement on the exciton binding energies has been systematically investigated for two series of ZnO/ZnMgO multiquantum wells with various well widths and barrier heights. The exciton binding energies were extracted from the energy difference between the stimulated emission band induced by inelastic exciton–exciton scattering and the free exciton absorption band. The binding energies of excitons are found to be sensitively dependent on the well widths. The experimental results of the well width dependence of binding energies are in good agreement with Coli and Bajaj’s theoretical calculations for these structures [G. Coli and K. K. Bajaj, Appl. Phys. Lett. 78, 2861 (2001)]. The remarkable reduction in coupling strength between excitons and longitudinal optical phonons is closely correlated with the enhancement of the exciton binding energy, indicating that the stability of excitons is greatly increased by the enhancement of exciton binding energy in quantum wells.

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Y. Segawa

Papers

Band gap engineering based on MgxZn1−xO and CdyZn1−yO ternary alloy films

Structure and optical properties of zno/mg0.2zn0.8o superlattices

Single crystalline ZnO films grown on lattice-matched ScAlMgO4(0001) substrates

Correlation between the photoluminescence lifetime and defect density in bulk and epitaxial ZnO

Enhancement of exciton binding energies in ZnO/ZnMgO multiquantum wells