Buckminsterfullerene hybridized zinc oxide tetrapods: defects and charge transfer induced optical and electrical response.

Buckminster fullerene (C60) based hybrid metal oxide materials are receiving considerable attention because of their excellent fundamental and applied aspects, like semiconducting, electron transfer, luminescent behaviors, etc. and this work briefly discusses the successful fabrication of C60 decorated ZnO tetrapod materials and their detailed structure-property relationships including device sensing applications. The electron microscopy investigations indicate that a quite dense surface coverage of ZnO tetrapods with C60 clusters is achieved. The spectroscopy studies confirmed the identification of the C60 vibrational modes and the C60 induced changes in the absorption and luminescence properties of the ZnO tetrapods. An increased C60 concentration on ZnO results in steeper ZnO bandgap absorption followed by well-defined free exciton and 3.31 eV line emissions. As expected, higher amounts of C60 increase the intensity of C60-related visible absorption bands. Pumping the samples with photons with an energy corresponding to these absorption band maxima leads to additional emission from ZnO showing an effective charge transfer phenomenon from C60 to the ZnO host. The density of states model obtained from DFT studies for pure and C60 coated ZnO surfaces confirms the experimental observations. The fabricated C60-ZnO hybrid tetrapod based micro- and nanodevices showed interesting ethanol gas sensing characteristics.

Fluctuating potentials in GaAs:Si nanowires: critical reduction of the influence of polytypism on the electronic structure.

In this work, the effects of Si doping in GaAs nanowires (NWs) grown on GaAs (111)B by molecular beam epitaxy with different Si doping levels (nominal free carrier concentrations of 1 × 1016, 8 × 1016, 1 × 1018 and 5 × 1018 cm-3) are deeply investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), grazing incidence X-ray diffraction (GID), photoluminescence (PL) and cathadoluminescence (CL). TEM results reveal a mixture of wurtzite (WZ) and zinc-blende (ZB) segments along the NW axis independently of the Si doping levels. GID measurements suggest a slight increase of the ZB fraction with the Si doping. Low temperature PL and CL spectra exhibit sharp lines in the energy range 1.41-1.48 eV, for the samples with lower Si doping levels. However, the emission intensity increases and is accompanied by a clear broadening of the observed lines for the samples with higher Si doping levels. The staggered type-II band alignment only determines the optical properties of the lower doping levels in GaAs:Si NWs. For the higher Si doping levels, the electronic energy level structure of the NWs is determined by electrostatic fluctuating potentials intimately related to the amphoteric behavior of the Si dopant in GaAs. For the heavily doped NWs, the estimated depth of the potential wells is ∼96-117 meV. Our results reveal that the occurrence of the fluctuating potentials is not dependent on the crystalline phase and shows that the limitation imposed by the polytypism can be overcome.

Hybridization of Zinc Oxide Tetrapods for Selective Gas Sensing Applications.

In this work, the exceptionally improved sensing capability of highly porous three-dimensional (3-D) hybrid ceramic networks toward reducing gases is demonstrated for the first time. The 3-D hybrid ceramic networks are based on doped metal oxides (MexOy and ZnxMe1-xOy, Me = Fe, Cu, Al) and alloyed zinc oxide tetrapods (ZnO-T) forming numerous junctions and heterojunctions. A change in morphology of the samples and formation of different complex microstructures is achieved by mixing the metallic (Fe, Cu, Al) microparticles with ZnO-T grown by the flame transport synthesis (FTS) in different weight ratios (ZnO-T:Me, e.g., 20:1) followed by subsequent thermal annealing in air. The gas sensing studies reveal the possibility to control and change/tune the selectivity of the materials, depending on the elemental content ratio and the type of added metal oxide in the 3-D ZnO-T hybrid networks. While pristine ZnO-T networks showed a good response to H2 gas, a change/tune in selectivity to ethanol vapor with a decrease in optimal operating temperature was observed in the networks hybridized with Fe-oxide and Cu-oxide. In the case of hybridization with ZnAl2O4, an improvement of H2 gas response (to ∼7.5) was reached at lower doping concentrations (20:1), whereas the increase in concentration of ZnAl2O4 (ZnO-T:Al, 10:1), the selectivity changes to methane CH4 gas (response is about 28). Selectivity tuning to different gases is attributed to the catalytic properties of the metal oxides after hybridization, while the gas sensitivity improvement is mainly associated with additional modulation of the electrical resistance by the built-in potential barriers between n-n and n-p heterojunctions, during adsorption and desorption of gaseous species. Density functional theory based calculations provided the mechanistic insights into the interactions between different hybrid networks and gas molecules to support the experimentally observed results. The studied networked materials and sensor structures performances would provide particular advantages in the field of fundamental research, applied physics studies, and industrial and ecological applications.

Photoluminescence studies of a perceived white light emission from a monolithic InGaN/GaN quantum well structure.

In this work we demonstrate by photoluminescence studies white light emission from a monolithic InGaN/GaN single quantum well structure grown by metal organic chemical vapour deposition. As-grown and thermally annealed samples at high temperature (1000 °C, 1100 °C and 1200 °C) and high pressure (1.1 GPa) were analysed by spectroscopic techniques, and the annealing effect on the photoluminescence is deeply explored. Under laser excitation of 3.8 eV at room temperature, the as-grown structure exhibits two main emission bands: a yellow band peaked at 2.14 eV and a blue band peaked at 2.8 eV resulting in white light perception. Interestingly, the stability of the white light is preserved after annealing at the lowest temperature (1000 °C), but suppressed for higher temperatures due to a deterioration of the blue quantum well emission. Moreover, the control of the yellow/blue bands intensity ratio, responsible for the white colour coordinate temperatures, could be achieved after annealing at 1000 °C. The room temperature white emission is studied as a function of incident power density, and the correlated colour temperature values are found to be in the warm white range: 3260-4000 K.

Luminescence studies on SnO2 and SnO2:Eu nanocrystals grown by laser assisted flow deposition.

Transparent conductive tin oxide materials have been a research topic extensively studied in recent years due to the great interest for many applications. However, in most of them, the pure form is rarely used, being usually modified by the incorporation of dopants. Selecting the most appropriate technique to develop nanocrystals of doped tin oxide and understanding the influence of dopant on the optical properties are the challenges that need to be addressed when envisaging devices. To fulfill this objective, the recently developed laser assisted flow deposition (LAFD) method is explored to grow SnO2 and SnO2:Eu nanocrystals. The morphology of these nanocrystals was investigated by scanning electron microscopy and well defined prismatic nanocrystals with sizes of ∼60 nm were identified. The crystalline quality assessed by X-ray diffraction measurements and Raman spectroscopy indicates that the produced nanocrystals are monophasic and crystallize in the tetragonal rutile structure. Steady state luminescence studies provide the information on the optical active centres in the SnO2 and SnO2:Eu nanocrystals. For the undoped samples only broad emission bands were observed by pumping the samples in the ultraviolet region. The broad emission was found to be an overlap of green and red optical centres as identified by temperature and excitation intensity dependent luminescence. The latter was found to exhibit an excitonic-related behaviour and the green emission was found to be of utmost importance to discuss the intraionic luminescence in the doped samples. For the SnO2:Eu nanocrystals the luminescence is dominated by the magnetic allowed (5)D0 → (7)F1 transition with the ions in almost undistorted centrosymmetric sites. The ion luminescence integrated intensity is found to increase with increasing temperatures being well accounted for a thermal population provided by the thermal quenching of the green band.