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

p-Type ZnO materials: Theory, growth, properties and devices

Abstract In the past 10 years, ZnO as a semiconductor has attracted considerable attention due to its unique properties, such as high electron mobility, wide and direct band gap and large exciton binding energy. ZnO has been considered a promising material for optoelectronic device applications, and the fabrications of high quality p-type ZnO and p–n junction are the key steps to realize these applications. However, the reliable p-type doping of the material remains a major challenge because of the self-compensation from native donor defects (V O and Zn i ) and/or hydrogen incorporation. Considerable efforts have been made to obtain p-type ZnO by doping different elements with various techniques. Remarkable progresses have been achieved, both theoretically and experimentally. In this paper, we discuss p-type ZnO materials: theory, growth, properties and devices, comprehensively. We first discuss the native defects in ZnO. Among the native defects in ZnO, V Zn and O i act as acceptors. We then present the theory of p-type doping in ZnO, and summarize the growth techniques for p-type ZnO and the properties of p-type ZnO materials. Theoretically, the principles of selection of p-type dopant, codoping method and X Zn –2V Zn acceptor model are introduced. Experimentally, besides the intrinsic p-type ZnO grown at O-rich ambient, p-type ZnO (MgZnO) materials have been prepared by various techniques using Group-I, IV and V elements. We pay a special attention to the band gap of p-type ZnO by band-gap engineering and room temperature ferromagnetism observed in p-type ZnO. Finally, we summarize the devices based on p-type ZnO materials.

RaoP-Type ZnO Materials: Theory, Growth, Properties, and Devices

The pathway towards the realization of optical solid-state lasers was gradual and slow. After Einstein's paper on absorption and stimulated emission of light in 1917 it took until 1960 for the first solid state laser device to see the light. Not much later, the first semiconductor laser was demonstrated and lasing in the near UV spectral range from ZnO was reported as early as 1966. The research on the optical properties of ZnO showed a remarkable revival since 1995 with the demonstration of room temperature lasing, which was further enhanced by the first report of lasing by a single nanowire in 2001. Since then, the research focussed increasingly on one-dimensional nanowires of ZnO. We start this review with a brief description of the opto-electronic properties of ZnO that are related to the wurtzite crystal structure. How these properties are modified by the nanowire geometry is discussed in the subsequent sections, in which we present the confined photon and/or polariton modes and how these can be investigated experimentally. Next, we review experimental studies of laser emission from single ZnO nanowires under different experimental conditions. We emphasize the special features resulting from the sub-wavelength dimensions by presenting our results on single ZnO nanowires lying on a substrate. At present, the mechanism of lasing in ZnO (nanowires) is the subject of a strong debate that is considered at the end of this review.

ZnO nanowire lasers

We have grown nitrogen-doped MgxZn1−xO:N films on Zn-polar ZnO single crystal substrates by molecular beam epitaxy. As N-sources, we employed NO-plasma or NH3 gas itself. As x increased, optimum growth temperature window for smooth film morphology shifted to higher temperatures, while maintaining high N-concentration (∼1×1019 cm−3). The heterosructures of MgxZn1−xO:N (0.1≤x≤0.4)/ZnO were fabricated into light emitting diodes of 500-μm-diameter. We observed ultraviolet near-band-edge emission (λ∼382 nm) with an output power of 0.1 μW for a NO-plasma-doped LED and 70 μW for a NH3-doped one at a bias current of 30 mA.

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Nitrogen doped MgxZn1−xO/ZnO single heterostructure ultraviolet light-emitting diodes on ZnO substrates

The excellent structural and optical properties of pseudomorphic MgxZn1-xO films (0≤x≤0.39) are reported in this work. The MgxZn1-xO films were grown on Zn-polar ZnO substrates by plasma-assisted molecular beam epitaxy. Those MgxZn1-xO films for which x≤0.18 exhibited atomically flat surfaces, and the typical full-width-at-half-maximum (FWHM) value of the (0002) X-ray diffraction ω-rocking curves for these films was 35 arcsec. The FWHM values were less than 100 meV for the near-band-edge photoluminescence (PL) at 300 K. We observed PL lifetimes of the order of ns, and the longest fast-decay component reached 3.5 ns for the Mg0.12Zn0.88O alloy.

http://iopscience.iop.org/article/10.1143/APEX.1.091202/pdf

Plasma-assisted Molecular Beam Epitaxy of High Optical Quality MgZnO Films on Zn-polar ZnO Substrates

MgxZn1-xO epitaxial films grown on ZnO substrates by molecular beam epitaxy - art. no. 68950D

Thin films of ZnO and Mg x Zn 1-x O were epitaxially grown on Zn-polar ZnO substrates by plasma assisted
molecular beam epitaxy. The miscut of c-plane ZnO substrates toward the [1-100] axis direction leads to a flat substrate
surface with straight step edges. The growth mode of epitaxial ZnO films significantly depended on the growth
temperature, and a substrate temperature over 800°C was needed for flat film surfaces with monolayer-height steps.
Photoluminescence (PL) peak originating from the n = 2 state of A-free excitons was observed at 12 K for the ZnO films
grown under stoichiometric and O-rich growth conditions. Mg x Zn 1-x O films were also fabricated under Zn-rich
conditions. The film surface exhibited a step-and-terrace structure. The effective PL lifetime of Mg 0.08 Zn 0.92 O film was as
long as 1.9 ns, which is the highest value ever reported, presumably due to a high purity level of the film.

MgxZn1-xO epitaxial films grown on ZnO substrates by molecular beam epitaxy

PROBLEM TO BE SOLVED: To provide an original-reading apparatus or the like, capable of suppressing changes in the level of a cable interconnecting a light source and a light emission control section, when emitting light by switching light sources. SOLUTION: The original reading apparatus includes a plurality of the LED light sources for emitting lights in different colors; the light emission control section, connected to a plurality of the LED light sources via the cable and for supplying electricity to the LED light sources to light up one LED light source among a plurality of the LED light sources and to allow the LED light source to emit light, and reads the original, by using a reflected light in the original receiving the light emitted by the LED light source. The light emission control section has an anode side switch connected to anodes of a plurality of the LED light sources via the cable, and each of the LED light sources is turned on, by turning on the anode side switch and turned off by turning off the anode side switch. COPYRIGHT: (C)2005,JPO&NCIPI

Atsushi Sasaki

Papers

Nitrogen doped MgxZn1−xO/ZnO single heterostructure ultraviolet light-emitting diodes on ZnO substrates

Plasma-assisted Molecular Beam Epitaxy of High Optical Quality MgZnO Films on Zn-polar ZnO Substrates

MgxZn1-xO epitaxial films grown on ZnO substrates by molecular beam epitaxy - art. no. 68950D

MgxZn1-xO epitaxial films grown on ZnO substrates by molecular beam epitaxy

Original-reading apparatus, computer program, original-reading system, and original-reading method