B. Postels

Zinc oxide nanorod based photonic devices: recent progress in growth, light?emitting diodes and lasers

Zinc oxide (ZnO), with its excellent luminescent properties and the ease of growth of its nanostructures, holds promise for the development of photonic devices. The recent advances in growth of ZnO nanorods are discussed. Results from both low temperature and high temperature growth approaches are presented. The techniques which are presented include metal-organic chemical vapour deposition (MOCVD), vapour phase epitaxy (VPE), pulse laser deposition (PLD), vapour-liquid-solid (VLS), aqueous chemical growth (ACG) and finally the electrodeposition technique as an example of a selective growth approach. Results from structural as well as optical properties of a variety of ZnO nanorods are shown and analysed using different techniques, including high resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), photoluminescence (PL) and cathodoluminescence (CL), for both room temperature and for low temperature performance. These results indicate that the grown ZnO nanorods possess reproducible and interesting optical properties. Results on obtaining p-type doping in ZnO micro- and nanorods are also demonstrated using PLD. Three independent indications were found for p-type conducting, phosphorus-doped ZnO nanorods: first, acceptor-related CL peaks, second, opposite transfer characteristics of back-gate field effect transistors using undoped and phosphorus doped wire channels, and finally, rectifying I-V characteristics of ZnO:P nanowire/ZnO:Ga p-n junctions. Then light emitting diodes (LEDs) based on n-ZnO nanorods combined with different technologies (hybrid technologies) are suggested and the recent electrical, as well as electro-optical, characteristics of these LEDs are shown and discussed. The hybrid LEDs reviewed and discussed here are mainly presented for two groups: those based on n-ZnO nanorods and p-type crystalline substrates, and those based on n-ZnO nanorods and p-type amorphous substrates. Promising electroluminescence characteristics aimed at the development of white LEDs are demonstrated. Although some of the presented LEDs show visible emission for applied biases in excess of 10 V, optimized structures are expected to provide the same emission at much lower voltage. Finally, lasing from ZnO nanorods is briefly reviewed. An example of a recent whispering gallery mode (WGM) lasing from ZnO is demonstrated as a way to enhance the stimulated emission from small size structures.

Origin of the near-band-edge photoluminescence emission in aqueous chemically grown ZnO nanorods

The optical properties of ZnO nanorods realized by an advanced low-temperature aqueous chemical growth on both silicon and plastic substrates are presented. Systematic photoluminescence investigations in the temperature range of 4–293K reveal strong and well-resolved near-band-edge emission even for rods on plastic substrate, and a weak deep-level emission. At intermediate temperatures phonon replicas of excitonic lines are observable. The optimum molar concentration range of the solution for obtaining nanorods of good optical quality is shown to lie between 0.025M and 0.075M. The large linewidth of the near-band-edge emission (∼10meV), its temperature dependence, and the absence of sharp excitonic transitions indicate that this emission is a result of transitions from a band of donor states.

Influence of ZnO seed crystals and annealing on the optical quality of low-temperature grown ZnO nanorods

The influence of ZnO seed crystals and postgrowth annealing on low-temperature aqueous chemically grown ZnO nanorods is analyzed. At the seed crystal/nanorod interface a high density of structural defects leads to emission at 3.332 eV, attributed to excitons bound to structural defects. This peak is absent for seed crystals, very pronounced for rods of shorter lengths grown on seed crystals, and reduced for longer nanorods. After annealing in oxygen and nitrogen atmosphere, the near-band-edge excitonic transitions sharpen and deep-level emission is strongly reduced. Time-resolved photoluminescence measurements show a striking similarity between donor-bound excitons and excitons bound to structural defects.

Controlled low-temperature fabrication of ZnO nanopillars with a wet-chemical approach

Aqueous chemical growth (ACG) is an efficient way to generate wafer-scale and densely packed arrays of ZnO nanopillars on various substrate materials. ACG is a low-temperature growth approach that is only weakly influenced by the substrate and even allows growth on flexible polymer substrates or on conducting materials. The advanced fabrication of wafer-scale and highly vertically aligned arrays of ZnO nanopillars on various substrate materials is demonstrated. Moreover, it is possible to control the morphology in diameter and length by changing the growth conditions. Photoluminescence characterization clearly shows a comparatively strong band-edge luminescence, even at room temperature, that is accompanied by a rather weak visible luminescence in the yellow/orange spectral range.

Properties of V-implanted ZnO nanorods

ZnO nanorods were grown on Si substrates by an aqueous chemical approach and subsequently doped by V implantation. Transmission electron microscopy and photoluminescence spectroscopy reveal a severely defective material directly after the implantation process. Subsequent annealing leads to a partial recovery of the crystal structure. The magnetic features of ZnO:V nanorods were investigated by magnetic force microscopy. Images taken of ensembles as well as of single rods clearly display contrast, which is seen as a strong indication of ferromagnetism at room temperature.

MOVPE gallium-nitride nanostructures fabricated on ZnO nanorod templates grown from aqueous chemical solution

Concerning optoelectronic devices fabricated by epitaxial methods, the combination of ZnO and GaN has promising aspects regarding their good optical properties and a relatively good lattice matching between both as compared to other foreign substrates like sapphire or silicon. Moreover ZnO nanopillar arrays may serve as a template for GaN nanopillar fabrication or for high quality GaN layers by lateral overgrowth of the ZnO nanopillars. In this work, we investigate the combination of two very different growth methods – aqueous chemical low temperature growth (ACG) for the ZnO nanopillar templates on silicon substrates and metalorganic vapor phase epitaxy (MOVPE) for the GaN overgrowth – in order to show to which extent the very cost efficient ZnO templates suit the high demands of GaN MOVPE. By a combination of annealing and photoluminescence experiments we show that the properties of the heterostructures change significantly with temperature.

Optical Characterisation of Low‐Temperature Grown ZnO Nanorods

Photoluminescence studies have been carried out on ZnO nanorods from an aqueous chemical growth. The results reveal well‐resolved near‐band‐edge emission with a broad linewidth of about 10 meV. Nanorods of different lengths and diameters on Si and even on plastic substrates showed similar optical properties indicating a good control of the growth process without much influence on the optical properties. Time‐resolved photoluminescence measurements show a very fast decay time of about 70 ps for the as‐grown samples but longer decay time of about 175 ps for the annealed samples.