M.O. Henry

Correlation of Raman and X-ray diffraction measurements of annealed pulsed laser deposited ZnO thin films

Abstract Raman spectroscopy, X-ray diffractometry and atomic force microscopy have been used to characterise ZnO thin films grown by pulsed laser deposition as a function of the post-growth annealing temperature. The results show substantial enhancement and broadening of certain Raman features which correlate excellently with the change in width of the X-ray diffraction peaks. The 570 cm−1 Raman feature showed pronounced asymmetry and enhanced intensity in the unannealed sample. An increase in grain size observed after subsequent annealing produced a substantial reduction in both the asymmetry and intensity of this peak. Our experimental data suggest that electric fields, due to charge trapping at grain boundaries, in conjunction with localised and surface phonon modes are the cause of the intensity enhancement and asymmetry of this feature.

Control of ZnO nanorod array density by Zn supersaturation variation and effects on field emission

We demonstrate control of ZnO nanorod density for self-organized growth on ZnO buffer layers on Si by varying Zn supersaturation during the initial growth phase, thereby altering the competition between 2D and 1D growth modes. Higher initial supersaturation favours nanorods of diameter 1000, attributed to sharp facet edges, and indicate that lower density arrays have more uniform emission due to a reduction in screening effects.

Growth of ZnO nanostructures on Au-coated Si: Influence of growth temperature on growth mechanism and morphology

ZnO nanostructures were grown on Au-catalyzed Si silicon substrates using vapor phase transport at growth temperatures from 800 to 1150 °C. The sample location ensured a low Zn vapor supersaturation during growth. Nanostructures grown at 800 and 850 °C showed a faceted rodlike morphology with mainly one-dimensional (1D) growth along the nanorod axis. Samples grown at intermediate temperatures (900, 950, and 1050 °C) in all cases showed significant three dimensional (3D) growth at the base of 1D nanostructures. At higher growth temperatures (1100 and 1150 °C) 3D growth tended to dominate resulting in the formation of a porous, nanostructured morphology. In all cases growth was seen only on the Au-coated region. Our results show that the majority of the nanostructures grow via a vapor-solid mechanism at low growth temperatures with no evidence of Au nanoparticles at their tip, in sharp contrast to the morphology expected for the vapor-liquid-solid (VLS) process often reported as the growth mechanism on Au-c...

ZnO films grown by pulsed-laser deposition on soda lime glass substrates for the ultraviolet inactivation of Staphylococcus epidermidis biofilms

Abstract We found that a ZnO film of 2 μm thickness which was laser-deposited at room temperature onto a plain soda lime glass substrate, exhibits notable antibacterial activity against a biofilm of Staphylococcus epidermidis when back-illuminated by a UVA light source with a peak emission wavelength of about 365 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-visible absorption spectroscopy, Raman spectroscopy and x-ray photoemission spectroscopy (XPS) were used to characterize the ZnO films before and after the interactions with the biofilm and the ultraviolet light, respectively. The as-deposited film was highly textured with the wurtzite (0002) in-plane orientation (c-axis perpendicular to ZnO surface) and had a surface rms roughness of 49.7 nm. In the as-deposited film, the Zn to O ratio was 1 to 0.95. After the UV and biofilm treatments, the ZnO film surface had become rougher (rms roughness 68.1 nm) and presented uniform micron-sized pitting randomly distributed, while the zinc to oxygen ratio had become 1 to 2.2. In this case, both the UV-visible and Raman spectra pointed to degradation of the structural quality of the material. On the strength of these data, we propose a model for the mediation of the bactericidal activity in which the photogeneration of highly oxidizing species and the presence of active surface defect sites both play an important role. This study is of particular interest for the acute problem of disinfection of pathogenic biofilms which form on medical device/implant surfaces.

Carbothermal reduction vapor phase transport growth of ZnO nanostructures: Effects of various carbon sources

ZnO nanostructures were grown via carbothermal reduction vapor phase transport with carbon black, activated carbon, and graphite powders. Nanostructures can be grown at significantly lower temperatures with carbon black and activated carbon, although with different morphologies compared to graphite. The surface areas of the carbon black and activated carbon are higher than those of graphite; this has been used previously to explain the origin of such growth and morphology differences. We use different ZnO∕graphite ratios to equalize surface areas compared to carbon black and eliminate this effect, but differences in nanostructure growth and morphology remain. We discuss the effects of thermodynamics and carbon purity and conclude that the high surface activities of the carbon black and activated carbon are the reason for our results.

(20−23) ZnO thin films grown by pulsed laser deposition on CeO2-buffered r-sapphire substrate

Composite ZnO∕CeO2 thin films were grown epitaxially on r-sapphire substrates using the pulsed laser deposition technique. Their crystalline properties were established using x-ray diffraction and showed the ZnO (wurtzite structure) and CeO2 (fluorite structure) layers to be highly textured with the (20−23) and (100) orientations, respectively. ϕ-scan measurements were also carried out and the (20−23)ZnO‖(100CeO2), [1−210]ZnO‖⟨011⟩ CeO2 epitaxial relations established. The rocking curve profiles indicated that the ZnO films grew as four crystallographically equivalent domains. Series of rocking curve and χ−scan measurements at varying ϕ angles, respectively, were used to investigate the domain structure. These showed that the normal to the (20−23) plane in each domain is tilted away from the substrate normal towards one of the four equivalent CeO2 ⟨111⟩ directions by ∼1.60. Atomic force microscopy measurements showed that the ZnO∕CeO2 composite film has a granular microstructure with a rough surface (typi...

Photoluminescence of deep defects involving transition metals in Si: New insights from highly enriched 28Si

Deep luminescence centers in Si associated with transition metals have been studied for decades, both as markers for these deleterious contaminants, as well as for the possibility of efficient Si-based light emission. They are among the most ubiquitous luminescence centers observed in Si, and have served as testbeds for elucidating the physics of isoelectronic bound excitons, and for testing ab-initio calculations of defect properties. The greatly improved spectral resolution resulting from the elimination of inhomogeneous isotope broadening in the recently available highly enriched 28Si enabled the extension of the established technique of isotope shifts to the measurement of isotopic fingerprints, which reveal not only the presence of a given element in a luminescence center, but also the number of atoms of that element. This has resulted in many surprises regarding the actual constituents of what were thought to be well-understood deep luminescence centers. Here we summarize the available information f...

A catalyst-free and facile route to periodically ordered and c-axis aligned ZnO nanorod arrays on diverse substrates

In this work we present a method for the deposition of periodically ordered, c-axis aligned ZnO nanorod arrays. By using chemical bath deposited films in conjunction with silica templating through nanosphere monolayers, masks suitable for high temperature deposition are created. A vapour phase transport technique is then used to deposit ordered arrays, quickly and inexpensively in a manner ideal for low cost, scalable and reproducible growth on a diverse range of substrates.

Study of photoluminescence at 3.310 and 3.368 eV in GaN/sapphire(0001) and GaN/GaAs(001) grown by liquid-target pulsed-laser deposition

Epitaxial GaN films of thickness ∼1 μm have been grown on sapphire(0001) and GaAs(001) substrates using the liquid-target pulsed-laser-deposition technique in a 5 Torr nitrogen atmosphere. Detailed x-ray diffraction and photoluminescence studies were carried out for both types of samples. Significantly enhanced low-temperature photoluminescence emissions at 3.368 eV (I3) and 3.310 eV (I4) were observed for the material deposited on a GaAs(001) substrate at ∼800 °C. We propose a model to explain the emission mechanism for both lines in which the electrons and holes are confined in cubic inclusions within the hexagonal material, analogously to a type-I quantum well.

Unambiguous identification of the role of a single Cu atom in the ZnO structured green band

High quality and purity single crystal ZnO samples doped with single isotopes of (63)Cu and (65)Cu, with equal concentrations of both these isotopes, and with natural Cu using a wet chemical atomic substitution reaction and anneal were studied using low temperature optical spectroscopy. Our data on the zero phonon line of the structured green band in ZnO confirm unambiguously the involvement of a single Cu atom in this defect emission. These data allow us to confirm the main features of the assignment proposed by Dingle in 1969 and to comment further on the defect structure.