V. E. Sandana

Study of Au coated ZnO nanoarrays for surface enhanced Raman scattering chemical sensing

Eight 1 cm2 samples of self-organising zinc oxide (ZnO) nanopillar arrays with preferential vertical orientation were grown by pulsed laser deposition and then coated with 30 nm of Au using either thermal or electron-beam evaporation. Each sample had a different set of ZnO and Au growth conditions. The Au/ZnO nanoarrays were then tested for use in surface enhanced Raman scattering (SERS) detection of thiophenol molecules. The ratio of ISERS/IRaman was adopted as a measure of the SERS sensitivity and was found to vary from 1.7 to 23.7 within the 8 samples. The impact of the density, width, filling factor, orientation, homogeneity and shape of the nanostructures on the average SERS intensity and the within-wafer reproducibility of the SERS response were considered for 9 paired comparisons based on fixing all but one of the growth parameters for each pairing. Overall, smaller nanopillar width was found to correlate with stronger average SERS signal while more vertically aligned arrays with higher filling factors showed better within-wafer reproducibility.

ZnO thin films and nanostructures for emerging optoelectronic applications

ZnO-based thin films and nanostructures grown by PLD for various emerging optoelectronic applications. AZO thin films are currently displacing ITO for many TCO applications due to recent improvements in attainable AZO conductivity combined with processing, cost and toxicity advantages. Advances in the channel mobilities and Id on/off ratios in ZnO-based TTFTs have opened up the potential for use as a replacement for a-Si in AM-OLED and AM-LCD screens. Angular-dependent specular reflection measurements of self-forming, moth-eye-like, nanostructure arrays grown by PLD were seen to have <0.5% reflectivity over the whole visible spectrum for angles of incidence between 10 and 60 degrees. Such nanostructures may be useful for applications such as AR coatings on solar cells. Compliant ZnO layers on mismatched/amorphous substrates were shown to have potential for MOVPE regrowth of GaN. This approach could be used as a means to facilitate lift-off of GaN-based LEDs from insulating sapphire substrates and could allow the growth of InGaN-based solar cells on cheap substrates. The green gap in InGaN-based LEDs was combated by substituting low Ts PLD n-ZnO for MOCVD n-GaN in inverted hybrid heterojunctions. This approach maintained the integrity of the InGaN MQWs and gave LEDs with green emission at just over 510 nm. Hybrid n-ZnO/p-GaN heterojunctions were also seen to have the potential for UV (375 nm) EL, characteristic of ZnO NBE emission. This suggests that there was significant hole injection into the ZnO and that such LEDs could profit from the relatively high exciton binding energy of ZnO.

Novel process for direct bonding of GaN onto glass substrates using sacrificial ZnO template layers to chemically lift-off GaN from c-sapphire

GaN was grown on ZnO-buffered c-sapphire (c-Al2O3) substrates by Metal Organic Vapor Phase Epitaxy. The ZnO then served as a sacrificial release layer, allowing chemical lift-off of the GaN from the c-Al2O3 substrate via selective wet etching of the ZnO. The GaN was subsequently direct-wafer-bonded onto a glass substrate. X-Ray Diffraction, Scanning Electron Microscopy, Energy Dispersive X-ray microanalysis, Room Temperature Photoluminescence & optical microscopy confirmed bonding of several mm2 of crack-free wurtzite GaN films onto a soda lime glass microscope slide with no obvious deterioration of the GaN morphology. Using such an approach, InGaN based devices can be lifted-off expensive single crystal substrates and bonded onto supports with a better cost-performance profile. Moreover, the approach offers the possibility of reclaiming and reusing the substrate.

MOCVD growth of ZnO nanostructures using Au droplets as catalysts

ZnO nanostructures were synthesised by Metal Organic Chemical Vapor Deposition growth on Si (100) and c-Al2O3 substrates coated with a 5nm thick layer of Au. The Au coated substrates were annealed in air prior to deposition of ZnO so as to promote formation of Au nanodroplets. The development of the nanodroplets was studied as a function of annealing duration and temperature. Under optimised conditions, a relatively homogeneous distribution of regular Au nanodroplets was obtained. Using the Au nanodroplets as a catalyst, MOCVD growth of ZnO nanostructures was studied. Scanning electron microscopy revealed nanostructures with various forms including commonly observed structures such as nanorods, nanoneedles and nanotubes. Some novel nanostructures were also observed, however, which resembled twist pastries and bevelled-multifaceted table legs.

Wafer-scale epitaxial lift-off of optoelectronic grade GaN from a GaN substrate using a sacrificial ZnO interlayer

Full 2 inch GaN epilayers were lifted off GaN and c-sapphire substrates by preferential chemical dissolution of sacrificial ZnO underlayers. Modification of the standard epitaxial lift-off (ELO) process by supporting the wax host with a glass substrate proved key in enabling full wafer scale-up. Scanning electron microscopy and x-ray diffraction confirmed that intact epitaxial GaN had been transferred to the glass host. Depth-resolved cathodoluminescence (CL) analysis of the bottom surface of the lifted-off GaN layer revealed strong near-band-edge (3.33 eV) emission indicating a superior optical quality for the GaN which was lifted off the GaN substrate. This modified ELO approach demonstrates that previous theories proposing that wax host curling was necessary to keep the ELO etch channel open do not apply to the GaN/ZnO system. The unprecedented full wafer transfer of epitaxial GaN to an alternative support by ELO offers the perspective of accelerating industrial adoption of the expensive GaN substrate through cost-reducing recycling.

Epitaxial MOVPE growth of highly c-axis oriented InGaN/GaN films on ZnO-buffered Si (111) substrates

InGaN/GaN layers were grown on ZnO-buffered Si (111) substrates by metalorganic vapour phase epitaxy (MOVPE). The dissociation of ZnO observed during conventional MOVPE growth of InGaN/GaN was combated through the use of a low pressure/temperature MOVPE approach with N2 as a carrier gas and dimethylhydrazine added to the ammonia (nitrogen precursor) in order to enhance the concentration of atomic nitrogen at relatively low temperature. Electron Microscopy of cross-sections, High Resolution X-Ray Diffraction (HR-XRD), secondary ion mass spectroscopy and cathodoluminescence studies suggested that single phase wurtzite InGaN layers with between about 17.5 and 21.5% indium were grown epitaxially, with no evidence of back-etching of the ZnO templates. HR-XRD revealed highly pronounced c-axis texture for both the InGaN/GaN and ZnO. Immersion in dilute nitric acid dissolved the ZnO such that the InGaN/GaN could be lifted-off from the substrate.

Nickel oxide growth on Si (111), c-Al2O3 and FTO/glass by pulsed laser deposition

NiO was grown on Si (111), c-Al2O3 and FTO/glass substrates by pulsed laser deposition (PLD). X-Ray Diffraction (XRD) and scanning electron microscope (SEM) studies revealed that layers grown on c-Al2O3 were fcc NiO with a dense morphology of cubic grains that were strongly (111) oriented along the growth direction. The relatively low ω rocking curve linewidth, of 0.12°suggests that there may have been epitaxial growth on the c-Al2O3 substrate. XRD and SEM indicated that films grown on Si (111) were also fcc NiO, with cubic grains, but that the grain orientation was random. This is consistent with the presence of an amorphous SiO2 layer at the surface of the Si substrate, which precluded epitaxial growth. NiO grown at lower temperature (200°C) on temperature-sensitive FTO/glass substrates showed no evidence of crystallinity in XRD and SEM studies. After flash annealing in air, however, peaks characteristic of randomly oriented fcc NiO appeared in the XRD scans and the surface morphology became more granular in appearance. Such layers appear promising for the development of future dye-sensitised solar cell devices based on NiO grown by PLD.

Comparison of chemical and laser lift-off for the transfer of InGaN-based p-i-n junctions from sapphire to glass substrates

InGaN-based p-i-n structures were transferred from sapphire to soda-lime glass substrates using two approaches: (1) laser-lift-off (LLO) and thermo-metallic bonding and (2) chemical lift-off (LLO) by means sacrificial ZnO templates and direct wafer bonding. Both processes were found to function at RT and allow reclaim of the expensive single crystal substrate. Both approaches have also already been demonstrated to work for the wafer-scale transfer of III/V semiconductors. Compared with the industry-standard LLO, the CLO offers the added advantages of a lattice match to InGaN with higher indium contents, no need for an interfacial adhesive layer (which facilitates electrical, optical and thermal coupling), no damaged/contaminated GaN surface layer, simplified sapphire reclaim (GaN residue after LLO may complicate reclaim) and cost savings linked to elimination of the expensive LLO process.

A study into the impact of sapphire substrate orientation on the properties of nominally-undoped β-Ga2O3 thin films grown by pulsed laser deposition

Nominally-undoped Ga2O3 layers were deposited on a-, c- and r-plane sapphire substrates using pulsed laser deposition. Conventional x-ray diffraction analysis for films grown on a- and c-plane sapphire showed the layers to be in the β-Ga2O3 phase with preferential orientation of the (-201) axis along the growth direction. Pole figures revealed the film grown on r-plane sapphire to also be in theβ-Ga2O3 phase but with epitaxial offsets of 29.5°, 38.5° and 64° from the growth direction for the (-201) axis. Optical transmission spectroscopy indicated that the bandgap was ~5.2eV, for all the layers and that the transparency was > 80% in the visible wavelength range. Four point collinear resistivity and Van der Pauw based Hall measurements revealed the β-Ga2O3 layer on r-plane sapphire to be 4 orders of magnitude more conducting than layers grown on a- and c-plane sapphire under similar conditions. The absolute values of conductivity, carrier mobility and carrier concentration for the β-Ga2O3 layer on r-sapphire (at 20Ω-1.cm-1, 6 cm2/Vs and 1.7 x 1019 cm-3, respectively) all exceeded values found in the literature for nominally-undoped β-Ga2O3 thin films by at least an order of magnitude. Gas discharge optical emission spectroscopy compositional depth profiling for common shallow donor impurities (Cl, F, Si and Sn) did not indicate any discernable increase in their concentrations compared to background levels in the sapphire substrate. It is proposed that the fundamentally anisotropic conductivity in β-Ga2O3 combined with the epitaxial offset of the (-201) axis observed for the layer grown on r-plane sapphire may explain the much larger carrier concentration, electrical conductivity and mobility compared with layers having the (-201) axis aligned along the growth direction.

Graphene versus oxides for transparent electrode applications

Due to their combination of good electrical conductivity and optical transparency, Transparent Conducting Oxides (TCOs) are the most common choice as transparent electrodes for optoelectronics applications. In particular, devices, such as LEDs, LCDs, touch screens and solar cells typically employ indium tin oxide. However, indium has some significant drawbacks, including toxicity issues (which are hampering manufacturing), an increasing rarefication (due to a combination of relative scarcity and increasing demand [1]) and resulting price increases. Moreover, there is no satisfactory option at the moment for use as a p-type transparent contact. Thus alternative materials solutions are actively being sought. This review will compare the performance and perspectives of graphene with respect to TCOs for use in transparent conductor applications.