Mónica Tirado

Electrical transport and optical model of GaAs-AlInP core-shell nanowires

GaAs nanowires were passivated by AlInP shells grown by the Au-assisted vapor-liquid-solid method in a gas source molecular beam epitaxy system. Transmission electron microscopy confirmed a core-shell GaAs-AlInP structure. Current-voltage measurements on ensemble nanowires indicated improved carrier transport properties in the passivated nanowires as compared to their unpassivated counterpart. Similarly, individual nanowires showed improved photoluminescence intensity upon passivation. A detailed model is presented to quantify the observed improvements in nanowire conduction and luminescence in terms of a reduction in surface charge trap density and surface recombination velocity upon passivation. The model includes the effects of high-level injection, bulk recombination, and surface recombination. The model can be used as a tool for assessing various passivation methods.

ZnO nanowire co-growth on SiO2 and C by carbothermal reduction and vapour advection

Vertically aligned ZnO nanowires (NWs) were grown on Au-nanocluster-seeded amorphous SiO(2) films by the advective transport and deposition of Zn vapours obtained from the carbothermal reaction of graphite and ZnO powders. Both the NW volume and visible-to-UV photoluminescence ratio were found to be strong functions of, and hence could be tailored by, the (ZnO+C) source-SiO(2) substrate distance. We observe C flakes on the ZnO NWs/SiO(2) substrates which exhibit short NWs that developed on both sides. The SiO(2) and C substrates/NW interfaces were studied in detail to determine growth mechanisms. NWs on Au-seeded SiO(2) were promoted by a rough ZnO seed layer whose formation was catalysed by the Au clusters. In contrast, NWs grew without any seed on C. A correlation comprising three orders of magnitude between the visible-to-UV photoluminescence intensity ratio and the NW volume is found, which results from a characteristic Zn partial pressure profile that fixes both O deficiency defect concentration and growth rate.

Electrical characteristics of core–shell p–n GaAs nanowire structures with Te as the n-dopant

GaAs nanowire (NW)-based p-n photovoltaic devices, with two distinct p and n spatial distributions and where Te was the n-dopant, have been studied by impedance spectroscopy in the 10(3)-10(7) Hz frequency range and the - 1.5-1.5 V bias range. For a large n-core/p-shell overlap region within NWs in a coaxial geometry, the p-n junction properties (DC rectification and p-n depletion capacitance) are found to prevail. The impedance data at low bias for both NW devices show large frequency dispersions with relaxation frequencies that are compatible with carrier re-emission times from traps due to GaAs surface states. An increasing conductance with increasing frequency for low bias is observed, suggesting hopping transport through localized states. For large bias the conductance increases exponentially with bias and is frequency independent, indicating conduction through extended states in this regime.

Hierarchical ZnO nanostructures: Growth mechanisms and surface correlated photoluminescence

ZnO nanowires were grown by vapor-transport and deposition on Au nanocluster covered fused and thermal silica and c-Si. The nanowire size and density depended strongly on the substrate type. By decreasing the O2 to local Zn partial pressure ratio, the growth pattern changed to nanocombs and nanosheets. ZnO nanohedgehogs were found on bare c-Si. We observe a remarkable correlation between the defect to exciton photoluminescence intensity ratio and the nanostructures specific surface areas. These results indicate that changes in strain and O deficiency defects at surfaces are behind the observed morphology changes, one to two-dimensional growth transition, and corresponding luminescence.

Luminescence and electrical properties of single ZnO/MgO core/shell nanowires

To neutralise the influence of the surface of ZnO nanowires for photonics and optoelectronic applications, we have covered them with insulating MgO film and individually contacted them for electrical characterisation. We show that such a metal-insulator-semiconductor-type nanodevice exhibits a high diode ideality factor of 3.4 below 1 V. MgO shell passivates ZnO surface states and provides confining barriers to electrons and holes within the ZnO core, favouring excitonic ultraviolet radiative recombination, while suppressing defect-related luminescence in the visible and improving electrical conductivity. The results indicate the potential use of ZnO/MgO nanowires as a convenient building block for nano-optoelectronic devices.

Surface depletion and electrical transport model of AlInP-passivated GaAs nanowires

Fabrication, current?voltage characterization and analytical modeling of an AlInP-passivated GaAs nanowire (NW) ensemble device are presented. During fabrication, sonication was used as a novel and crucial step to ensure effective contacting of the NWs. Current?voltage characteristics of the passivated NW devices were fitted using an analytical surface depletion and transport model which improves upon established models by implementing a non-uniform density of GaAs surface states and including a NW diameter distribution. Scanning electron microscopy, capacitance?voltage characterization and secondary ion mass spectrometry were used to fix key parameters in the model. A 55% decrease in surface state density was achieved upon passivation, corresponding to an impressive four order of magnitude increase in the effective carrier concentration of the NWs. Moreover, the thickest NWs in the ensemble were found to dictate the device characteristics, which is a behavior that should be common to all ensemble NW devices with a distribution in radius. As final confirmation of effective passivation, time-resolved photoluminescence measurements showed a 25??improvement in carrier lifetime upon passivation. The fabrication and passivation methods can be easily implemented into future optoelectronic applications.

Enhanced optical properties and (Zn, Mg) interdiffusion in vapour transport grown ZnO/MgO core/shell nanowires

ZnO/MgO (core/shell) nanowires (NWs) grown by a two-step vapour transport method under different MgO shell growth conditions are examined by x-ray diffraction, photoluminescence (PL) excitation and temperature (10-300 K) dependent PL. The excitonic-to-defect PL ratio is increased by more than two orders of magnitude in the core/shell as compared to bare ZnO NWs. Concomitantly, a strong depression of the PL thermal quenching, most particularly for the visible part of the PL spectrum, occurs. Using a semi-quantitative model, results are interpreted as a strong radiative to non-radiative lifetime ratio reduction due to defect passivation at the ZnO NW walls and photocarrier confinement within the ZnO core by the MgO shell. These beneficial effects are, however, significantly weakened when metal interdiffusion across the core/shell interface is favoured during the shell growth. Non-radiative recombination lifetime in the sample with sharp core/shell interface is described by a single activation energy of 15 meV (bound exciton release). For interdiffused cases and bare ZnO an additional activation energy of 60 meV (free exciton breakup) is observed.

Glucose biosensor based on functionalized ZnO nanowire/graphite films dispersed on a Pt electrode.

We present a glucose biosensor based on ZnO nanowire self-sustained films grown on compacted graphite flakes by the vapor transport method. Nanowire/graphite films were fragmented in water, filtered to form a colloidal suspension, subsequently functionalized with glucose oxidase and finally transferred to a metal electrode (Pt). The obtained devices were evaluated using scanning electron microscopy, energy-dispersive x-ray spectroscopy, cyclic voltammetry and chronoamperometry. The electrochemical responses of the devices were determined in buffer solutions with successive glucose aggregates using a tripolar electrode system. The nanostructured biosensors showed excellent analytical performance, with linear response to glucose concentrations, high sensitivity of up to ≈17 μA cm(-2) mM(-1) in the 0.03-1.52 mM glucose concentration range, relatively low Michaelis-Menten constant, excellent reproducibility and a fast response. The detection limits are more than an order of magnitude lower than those achievable in commercial biosensors for glucose control, which is promising for the development of glucose monitoring methods that do not require blood extraction from potentially diabetic patients. The strong detection enhancements provided by the functionalized nanostructures are much larger than the electrode surface-area increase and are discussed in terms of the physical and chemical mechanisms involved in the detection and transduction processes.

Nonlinear excitation of polariton cavity modes in ZnO single nanocombs.

Tunable second harmonic (SH) polaritons have been efficiently generated in ZnO nanocombs, when the material is excited close to half of the band-gap. The nonlinear signal couples to the nanocavity modes, and, as a result, Fabry-Pérot resonances with high Q factors of about 500 are detected. Due to the low effective volume of the confined modes, matter-light interaction is very much enhanced. This effect lowers the velocity of the SH polariton in the material by 50 times, and increases the SH confinement inside the nanocavity due to this higher refractive index. We also show that the SH phase-matching condition is achieved through LO-phonon mediation. Finally, birrefringence of the crystal produces a strong SH intensity dependence on the input polarization, with a high polarization contrast, which could be used as a mechanism for light switching in the nanoscale.

The shell effect on the room temperature photoluminescence from ZnO/MgO core/shell nanowires: exciton–phonon coupling and strain

The room temperature photoluminescence from ZnO/MgO core/shell nanowires (NWs) grown by a simple two-step vapor transport method was studied for various MgO shell widths (w). Two distinct effects induced by the MgO shell were clearly identified. The first one, related to the ZnO/MgO interface formation, is evidenced by strong enhancements of the zero-phonon and first phonon replica of the excitonic emission, which are accompanied by a total suppression of its second phonon replica. This effect can be explained by the reduction of the band bending within the ZnO NW core that follows the removal of atmospheric adsorbates and associated surface traps during the MgO growth process on one hand, and a reduced exciton-phonon coupling as a result of the mechanical stabilization of the outermost ZnO NW monolayers by the MgO shell on the other hand. The second effect is the gradual increase of the excitonic emission and decrease in the defect related emission by up to two and one orders of magnitude, respectively, when w is increased in the ∼3-17 nm range. Uniaxial strain build-up within the ZnO NW core with increasing w, as detected by x-ray diffraction measurements, and photocarrier tunneling escape from the ZnO core through the MgO shell enabled by defect-states are proposed as possible mechanisms involved in this effect. These findings are expected to be of key significance for the efficient design and fabrication of ZnO/MgO NW heterostructures and devices.