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

Light-Emitting Diodes. (Monographs in Electrical and Electronic Engineering.) By A. A. Bergh and P. J. Dean. Pp. viii+591. (Clarendon: Oxford; Oxford University: London, 1976.) £22.

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Light-emitting diodes

One-dimensional (1D) ZnO nanostructures have been studied intensively and extensively over the last decade not only for their remarkable chemical and physical properties, but also for their current and future diverse technological applications. This article gives a comprehensive overview of the progress that has been made within the context of 1D ZnO nanostructures synthesized via wet chemical methods. We will cover the synthetic methodologies and corresponding growth mechanisms, different structures, doping and alloying, position-controlled growth on substrates, and finally, their functional properties as catalysts, hydrophobic surfaces, sensors, and in nanoelectronic, optical, optoelectronic, and energy harvesting devices.

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One-dimensional ZnO nanostructures: Solution growth and functional properties

ZnO nanostructures for optoelectronics: Material properties and device applications

Exploiting the low spatial coherence of specifically designed random lasers, researchers demonstrate speckle-free full-field imaging in the regime of intense optical scattering. Their results show that the quality of images generated from random-laser illumination is superior to those generated from spatially coherent illumination.

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Speckle-free laser imaging using random laser illumination

Ultraviolet semiconductor lasers are widely used for applications in photonics, information storage, biology and medical therapeutics. Although the performance of gallium nitride ultraviolet lasers has improved significantly over the past decade, demand for lower costs, higher powers and shorter wavelengths has motivated interest in zinc oxide (ZnO), which has a wide direct bandgap and a large exciton binding energy. ZnO-based random lasing has been demonstrated with both optical and electrical pumping, but random lasers suffer from reduced output powers, unstable emission spectra and beam divergence. Here, we demonstrate electrically pumped Fabry-Perot type waveguide lasing from laser diodes that consist of Sb-doped p-type ZnO nanowires and n-type ZnO thin films. The diodes exhibit highly stable lasing at room temperature, and can be modelled with finite-difference time-domain methods.

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Electrically pumped waveguide lasing from ZnO nanowires

Electrically pumped ZnO quantum well diode lasers are reported. Sb-doped p-type ZnO/Ga-doped n-type ZnO with an MgZnO/ZnO/MgZnO quantum well embedded in the junction was grown on Si by molecular beam epitaxy. The diodes emit lasing at room temperature with a very low threshold injection current density of 10 A/cm2. The lasing mechanism is exciton-related recombination and the feedback is provided by close-loop scattering from closely packed nanocolumnar ZnO grains formed on Si.

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Electrically pumped ultraviolet ZnO diode lasers on Si

ZnO p-n homojunction light emitting diodes were fabricated based on p-type Sb-doped ZnO∕n-type Ga-doped ZnO thin films. Low resistivity Au∕NiO and Au∕Ti contacts were formed on top of p-type and n-type ZnO layers, respectively. Au∕NiO contacts on p-type ZnO exhibited a low specific resistivity of 7.4×10−4Ωcm2. The light emitting diodes yielded strong near-band-edge emissions in temperature-dependent and injection current-dependent electroluminescence measurements.

Sb-doped p-ZnO∕Ga-doped n-ZnO homojunction ultraviolet light emitting diodes

Heterojunction light emitting diodes (LEDs) were fabricated by making Au∕Ni top Ohmic contacts on Sb-doped p-type ZnO film with low specific contact resistivity and Al∕Ti back Ohmic contacts on n-type Si substrate. Near-band edge and deep-level emissions were observed from the LED devices at both low temperatures and room temperature, which is due to band-to-band and band-to-deep level radiative recombinations in ZnO, respectively. The electroluminescence emissions precisely match those of photoluminescence spectra from Sb-doped p-type ZnO, indicating that the ZnO layer acts as the active region for the radiative recombinations of electrons and holes in the diode operation.

Ultraviolet emission from Sb-doped p-type ZnO based heterojunction light-emitting diodes

ZnO p-n homojunctions based on Sb-doped p-type nanowire array and n-type film were grown by combining chemical vapor deposition (for nanowires) with molecular-beam epitaxy (for film). Indium tin oxide and Ti/Au were used as contacts to the ZnO nanowires and film, respectively. Characteristics of field-effect transistors using ZnO nanowires as channels indicate p-type conductivity of the nanowires. Electron beam induced current profiling confirmed the existence of ZnO p-n homojunction. Rectifying I-V characteristic showed a turn-on voltage of around 3 V. Very good response to ultraviolet light illumination was observed from photocurrent measurements.

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Sheng Chu

Papers

Electrically pumped waveguide lasing from ZnO nanowires

Electrically pumped ultraviolet ZnO diode lasers on Si

Sb-doped p-ZnO∕Ga-doped n-ZnO homojunction ultraviolet light emitting diodes

Ultraviolet emission from Sb-doped p-type ZnO based heterojunction light-emitting diodes

ZnO homojunction photodiodes based on Sb-doped p-type nanowire array and n-type film for ultraviolet detection