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

The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry and properties of nanocrystals of different shapes.

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

Atomic layer deposition(ALD), a chemical vapor deposition technique based on sequential self-terminating gas–solid reactions, has for about four decades been applied for manufacturing conformal inorganic material layers with thickness down to the nanometer range. Despite the numerous successful applications of material growth by ALD, many physicochemical processes that control ALD growth are not yet sufficiently understood. To increase understanding of ALD processes, overviews are needed not only of the existing ALD processes and their applications, but also of the knowledge of the surface chemistry of specific ALD processes. This work aims to start the overviews on specific ALD processes by reviewing the experimental information available on the surface chemistry of the trimethylaluminum/water process. This process is generally known as a rather ideal ALD process, and plenty of information is available on its surface chemistry. This in-depth summary of the surface chemistry of one representative ALD process aims also to provide a view on the current status of understanding the surface chemistry of ALD, in general. The review starts by describing the basic characteristics of ALD, discussing the history of ALD—including the question who made the first ALD experiments—and giving an overview of the two-reactant ALD processes investigated to date. Second, the basic concepts related to the surface chemistry of ALD are described from a generic viewpoint applicable to all ALD processes based on compound reactants. This description includes physicochemical requirements for self-terminating reactions,reaction kinetics, typical chemisorption mechanisms, factors causing saturation, reasons for growth of less than a monolayer per cycle, effect of the temperature and number of cycles on the growth per cycle (GPC), and the growth mode. A comparison is made of three models available for estimating the sterically allowed value of GPC in ALD. Third, the experimental information on the surface chemistry in the trimethylaluminum/water ALD process are reviewed using the concepts developed in the second part of this review. The results are reviewed critically, with an aim to combine the information obtained in different types of investigations, such as growth experiments on flat substrates and reaction chemistry investigation on high-surface-area materials. Although the surface chemistry of the trimethylaluminum/water ALD process is rather well understood, systematic investigations of the reaction kinetics and the growth mode on different substrates are still missing. The last part of the review is devoted to discussing issues which may hamper surface chemistry investigations of ALD, such as problematic historical assumptions, nonstandard terminology, and the effect of experimental conditions on the surface chemistry of ALD. I hope that this review can help the newcomer get acquainted with the exciting and challenging field of surface chemistry of ALD and can serve as a useful guide for the specialist towards the fifth decade of ALD research.

Surface chemistry of atomic layer deposition: A case study for the trimethylaluminum/water process

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

Structural analysis was performed on a purple laser diode composed of In0.20Ga0.80N (3 nm)/ In0.05Ga0.95N (6 nm) multiple quantum wells, by employing transmission electron microscopy and energy-dispersive x-ray microanalysis, both of which are assessed from the cross-sectional direction. It was found that the contrast of light and shade in the well layers corresponds to the difference in In composition. The main radiative recombination was attributed to excitons localized at deep traps which probably originate from the In-rich region in the wells acting as quantum dots. Photopumped lasing was observed at the high energy side of the main spontaneous emission bands.

Role of self-formed InGaN quantum dots for exciton localization in the purple laser diode emitting at 420 nm

(201)-oriented β-Ga2O3 thin films were grown on c-plane sapphire substrates by plasma-assisted molecular beam epitaxy. In-plane X-ray diffraction measurements revealed the inclusion of α-Ga2O3 and rotational domains. However, the film grown under the optimized growth conditions exhibited a sharp absorption edge at around 5.0 eV, which is in the deep-ultraviolet region. An ohmic-type metal–semiconductor–metal photodetector showed a high resistance of around 6 GΩ with a small dark current of 1.2 nA at the 10 V bias voltage. Under 254 nm light illumination and 10 V bias voltage, the photoresponsivity was 0.037 A/W, which corresponded to a quantum efficiency of 18%.

https://iopscience.iop.org/article/10.1143/JJAP.46.7217/pdf

Ga2O3 thin film growth on c-plane sapphire substrates by molecular beam epitaxy for deep-ultraviolet photodetectors

Dynamical behavior of radiative recombination has been assessed in the ${\mathrm{In}}_{0.20}$${\mathrm{Ga}}_{0.80}$N (2.5 nm)/ ${\mathrm{In}}_{0.05}$${\mathrm{Ga}}_{0.95}$N (6.0 nm) multiple-quantum-well structure by means of transmittance, electroreflectance (ER), photoluminescence excitation (PLE), and time-resolved photoluminescence (TRPL) spectroscopy. The PL at 20 K was mainly composed of two emission bands whose peaks are located at 2.920 eV and 3.155 eV. Although the peak at 3.155 eV was weak under low photoexcitation, it grew superlinearly with increasing excitation intensity. The ER and PLE revealed that the transition at 3.155 eV is due to the excitons at quantized levels between n=1 conduction and n=1 A(${\mathrm{\ensuremath{\Gamma}}}_{9\mathrm{v}}$) valence bands, while the main PL peak at 2.920 eV is attributed to the excitons localized at the trap centers within the well. The TRPL features were well understood as the effect of localization where photogenerated excitons are transferred from the n=1 band to the localized centers, and then are localized further to the tail state.

Recombination dynamics of localized excitons in In 0.20 Ga 0.80 N- In 0.05 Ga 0.95 N multiple quantum wells

Al-doped ZnO (AZO) thin films have been prepared by mist chemical vapor deposition and magnetron sputtering. The band gap shift as a function of carrier concentration in n-type zinc oxide (ZnO) was systematically studied considering the available theoretical models. The shift in energy gap, evaluated from optical absorption spectra, did not depend on sample preparations; it was mainly related to the carrier concentrations and so intrinsic to AZO. The optical gap increased with the electron concentration approximately as ne2∕3 for ne≤4.2×1019 cm−3, which could be fully interpreted by a modified Burstein–Moss (BM) shift with the nonparabolicity of the conduction band. A sudden decrease in energy gap occurred at 5.4−8.4×1019 cm−3, consistent with the Mott criterion for a semiconductor-metal transition. Above the critical values, the band gap increased again at a different rate, which was presumably due to the competing BM band-filling and band gap renormalization effects, the former inducing a band gap widen...

Carrier concentration dependence of band gap shift in n-type ZnO:Al films

Ga2O3 thin films of the α-phase, that is, the corundum structure (in the trigonal system), have been epitaxially obtained on sapphire (α-Al2O3) substrates, in contrast to the strong tendency of Ga2O3 to assume a heterogeneous crystal structure, that is, the β-gallia structure (in the monoclinic system) on sapphire. This result is advantageous for high-quality films and is due to the growth by mist chemical vapor deposition (CVD) at low temperatures of 430–470 °C. The α-Ga2O3 films have narrow full-widths at half maximum (FWHMs) in their X-ray diffraction rocking curves, for example, about 60 arcsec. The root mean square (RMS) roughness of the surface was as small as 1 nm. The optical band gap energy obtained was 5.3 eV, and the films were almost completely transparent in the near-ultraviolet and visible regions. The epitaxial growth of α-Ga2O3 films on sapphire is beneficial for the fabrication of oxide optical and electronic devices.

https://iopscience.iop.org/article/10.1143/JJAP.47.7311/pdf

Shizuo Fujita

Papers

Role of self-formed InGaN quantum dots for exciton localization in the purple laser diode emitting at 420 nm

Ga2O3 thin film growth on c-plane sapphire substrates by molecular beam epitaxy for deep-ultraviolet photodetectors

Recombination dynamics of localized excitons in In 0.20 Ga 0.80 N- In 0.05 Ga 0.95 N multiple quantum wells

Carrier concentration dependence of band gap shift in n-type ZnO:Al films

Heteroepitaxy of Corundum-Structured α-Ga2O3 Thin Films on α-Al2O3 Substrates by Ultrasonic Mist Chemical Vapor Deposition