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 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.

Zinc oxide (ZnO) is a wide band gap semiconductor with potential applications in optoelectronics, transparent electronics, and spintronics. The high efficiency of UV emission in this material could be harnessed in solid-state white lighting devices. The problem of defects, in particular, acceptor dopants, remains a key challenge. In this review, defects in ZnO are discussed, with an emphasis on the physical properties of point defects in bulk crystals. As grown, ZnO is usually n-type, a property that was historically ascribed to native defects. However, experiments and theory have shown that O vacancies are deep donors, while Zn interstitials are too mobile to be stable at room temperature. Group-III (B, Al, Ga, and In) and H impurities account for most of the n-type conductivity in ZnO samples. Interstitial H donors have been observed with IR spectroscopy, while substitutional H donors have been predicted from first-principles calculations but not observed directly. Despite numerous reports, reliable p-t...

Defects in ZnO

Semiconducting quantum dots, whose particle sizes are in the nanometer range, have very unusual properties. The quantum dots have band gaps that depend in a complicated fashion upon a number of factors, described in the article. Processing-structure-properties-performance relationships are reviewed for compound semiconducting quantum dots. Various methods for synthesizing these quantum dots are discussed, as well as their resulting properties. Quantum states and confinement of their excitons may shift their optical absorption and emission energies. Such effects are important for tuning their luminescence stimulated by photons (photoluminescence) or electric field (electroluminescence). In this article, decoupling of quantum effects on excitation and emission are described, along with the use of quantum dots as sensitizers in phosphors. In addition, we reviewed the multimodal applications of quantum dots, including in electroluminescence device, solar cell and biological imaging.

https://www.mdpi.com/1996-1944/3/4/2260/pdf

Quantum Dots and Their Multimodal Applications: A Review

ZnO has emerged as a promising candidate for optoelectronic and microelectronic applications, whose development requires greater understanding and control of their electronic contacts. The rapid pace of ZnO research over the past decade has yielded considerable new information on the nature of ZnO interfaces with metals. Work on ZnO contacts over the past decade has now been carried out on high quality material, nearly free from complicating factors such as impurities, morphological and native point defects. Based on the high quality bulk and thin film crystals now available, ZnO exhibits a range of systematic interface electronic structure that can be understood at the atomic scale. Here we provide a comprehensive review of Schottky barrier and ohmic contacts including work extending over the past half century. For Schottky barriers, these results span the nature of ZnO surface charge transfer, the roles of surface cleaning, crystal quality, chemical interactions, and defect formation. For ohmic contacts...

ZnO Schottky barriers and Ohmic contacts

Reproducible Sb-doped p-type ZnO films were grown on n-Si (100) by electron-cyclotron-resonance-assisted molecular-beam epitaxy. The existence of Sb in ZnO:Sb films was confirmed by low-temperature photoluminescence measurements. An acceptor-bound exciton (A°X) emission was observed at 3.358 eV at 8 K. The acceptor energy level of the Sb dopant is estimated to be 0.2 eV above the valence band. Temperature-dependent Hall measurements were performed on Sb-doped ZnO films. At room temperature, one Sb-doped ZnO sample exhibited a low resistivity of 0.2Ωcm, high hole concentration of 1.7×1018cm−3 and high mobility of 20.0cm2∕Vs. This study suggests that Sb is an excellent dopant for reliable and reproducible p-type ZnO fabrication.

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High-mobility Sb-doped p-type ZnO by molecular-beam epitaxy

We investigated photoluminescence (PL) from reliable and reproducible Sb-doped p-type ZnO films grown on n-Si (100) by molecular-beam epitaxy. Well-resolved PL spectra were obtained from completely dopant-activated samples with hole concentrations above 1.0×1018cm−3. From free electron to acceptor transitions, acceptor binding energy of 0.14 eV is determined, which is in good agreement with analytical results of the temperature-dependent PL measurements. Another broad peak at 3.050 eV, which shifts to lower energy at higher temperatures, indicates the formation of deep acceptor level bands related to Zn vacancies, which are created by Sb doping.

Photoluminescence study of Sb-doped p-type ZnO films by molecular-beam epitaxy

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

Antimony (Sb) doping was used to realize p-type ZnO films on n-Si (100) substrates by molecular beam epitaxy. These samples were fabricated into p-n heterojunction diodes. p-type behavior of Sb-doped ZnO was studied by carrying out I-V and capacitance-voltage (C-V) measurements. I-V curves showed rectifying behavior similar to a p-type Schottky diode with a turn-on voltage around 2.4V, which is consistent with the Schottky barrier of about 2.2V obtained from C-V characterization. Good photoresponse in the UV region was obtained, which further proved that Sb doping could be used to fabricate p-type ZnO for photodetector and other optoelectronic applications.

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p-type behavior from Sb-doped ZnO heterojunction photodiodes

Phosphorus-doped p-type ZnO films were grown on r-plane sapphire substrates using molecular-beam epitaxy with a solid-source GaP effusion cell. X-ray diffraction spectra and reflection high-energy electron diffraction patterns indicate that high-quality single crystalline (112¯0) ZnO films were obtained. Hall and resistivity measurements show that the phosphorus-doped ZnO films have high hole concentrations and low resistivities at room temperature. Photoluminescence (PL) measurements at 8 K reveal a dominant acceptor-bound exciton emission with an energy of 3.317 eV. The acceptor energy level of the phosphorus dopant is estimated to be 0.18 eV above the valence band from PL spectra, which is also consistent with the temperature dependence of PL measurements.

http://www.physics.fudan.edu.cn/tps/people/fxxiu/publications/aplZno.pdf

L. J. Mandalapu

Papers

High-mobility Sb-doped p-type ZnO by molecular-beam epitaxy

Photoluminescence study of Sb-doped p-type ZnO films by molecular-beam epitaxy

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

p-type behavior from Sb-doped ZnO heterojunction photodiodes

p-type ZnO films with solid-source phosphorus doping by molecular-beam epitaxy