Focus on inorganic semiconductor nanowires for device applications

Anodically formed, vertically oriented, self-organized cylindrical TiO₂ nanotube arrays composed of the anatase phase undergo an interesting morphological and phase transition upon flame annealing to square-shaped nanotubes composed of both anatase and rutile phases. This is the first report on heterojunctions consisting of metal nanoparticles (NPs) deposited on square-shaped TiO₂ nanotube arrays (STNAs) with mixed rutile and anatase phase content. A simple photochemical deposition process was used to form Cu, CuPt, and Pt NPs on the STNAs, and an enhancement in the visible light photoelectrochemical water splitting performance for the NP-decorated STNAs was observed over the bare STNAs. Under narrow band illumination by visible photons at 410 nm and 505 nm, Cu NP-decorated STNAs performed the best, producing photocurrents 80% higher and 50 times higher than bare STNAs, respectively. Probing the energy level structure at the NP–STNA interface using ultraviolet photoelectron spectroscopy revealed Schottky barrier formation in the NP-decorated STNAs, which assists in separating the photogenerated charge carriers, as also confirmed by longer charge carrier lifetimes in NP-decorated STNAs. While all the NP-decorated STNAs showed enhanced visible light absorption compared to the bare STNAs, only the Cu NPs exhibited a clear plasmonic behavior with an extinction cross section that peaked at 550 nm.

We compare the characteristics of phase-pure MOCVD grown ZB and WZ InAs nanowire transistors in several atmospheres: air, dry pure N₂ and O₂, and N₂ bubbled through liquid H₂O and alcohols to identify whether phase-related structural/surface differences affect their response. Both WZ and ZB give poor gate characteristics in dry state. Adsorption of polar species reduces off-current by 2–3 orders of magnitude, increases on–off ratio and significantly reduces sub-threshold slope. The key difference is the greater sensitivity of WZ to low adsorbate level. We attribute this to facet structure and its influence on the separation between conduction electrons and surface adsorption sites. We highlight the important role adsorbed species play in nanowire device characterisation. WZ is commonly thought superior to ZB in InAs nanowire transistors. We show this is an artefact of the moderate humidity found in ambient laboratory conditions: WZ and ZB perform equally poorly in the dry gas limit yet equally well in the wet gas limit. We also highlight the vital role density-lowering disorder has in improving gate characteristics, be it stacking faults in mixed-phase WZ or surface adsorbates in pure-phase nanowires.

Compared to traditional pn-junction photovoltaics, hot carrier solar cells offer potentially higher efficiency by extracting work from the kinetic energy of photogenerated 'hot carriers' before they cool to the lattice temperature. Hot carrier solar cells have been demonstrated in high-bandgap ferroelectric insulators and GaAs/AlGaAs heterostructures, but so far not in low-bandgap materials, where the potential efficiency gain is highest. Recently, a high open-circuit voltage was demonstrated in an illuminated wurtzite InAs nanowire with a low bandgap of 0.39 eV, and was interpreted in terms of a photothermoelectric effect. Here, we point out that this device is a hot carrier solar cell and discuss its performance in those terms. In the demonstrated devices, InP heterostructures are used as energy filters in order to thermoelectrically harvest the energy of hot electrons photogenerated in InAs absorber segments. The obtained photovoltage depends on the heterostructure design of the energy filter and is therefore tunable. By using a high-resistance, thermionic barrier, an open-circuit voltage is obtained that is in excess of the Shockley–Queisser limit. These results provide generalizable insight into how to realize high voltage hot carrier solar cells in low-bandgap materials, and therefore are a step towards the demonstration of higher efficiency hot carrier solar cells.

ZnO radial p–n junction architecture has the potential for forward-leap of light-emitting diode (LED) technology in terms of higher efficacy and economical production. We report on ZnO radial p–n junction-based light emitting diodes prepared by full metalorganic chemical vapour deposition (MOCVD) with hydrogen-assisted p-type doping approach. The p-type ZnO(P) thin films were prepared by MOCVD with the precursors of dimethylzinc, tert-butanol, and tertiarybutylphosphine. Controlling the precursor flow for dopant results in the systematic change of doping concentration, Hall mobility, and electrical conductivity. Moreover, the approach of hydrogen-assisted phosphorous doping in ZnO expands the understanding of doping behaviour in ZnO. Ultraviolet and visible electroluminescence of ZnO radial p–n junction was demonstrated through a combination of position-controlled nano/microwire and crystalline p-type ZnO(P) radial shell growth on the wires. The reported research opens a pathway of realisation of production-compatible ZnO p–n junction LEDs.

This is the first report of a 17.6% champion efficiency solar cell architecture comprising monocrystalline TiO₂ nanorods (TNRs) coupled with perovskite, and formed using facile solution processing without non-routine surface conditioning. Vertically oriented TNR ensembles are desirable as electron transporting layers (ETLs) in halide perovskite solar cells (HPSCs) because of potential advantages such as vectorial electron percolation pathways to balance the longer hole diffusion lengths in certain halide perovskite semiconductors, ease of incorporating nanophotonic enhancements, and optimization between a high contact surface area for charge transfer (good) versus high interfacial recombination (bad). These advantages arise from the tunable morphology of hydrothermally grown rutile TNRs, which is a strong function of the growth conditions. Fluorescence lifetime imaging microscopy of the HPSCs demonstrated a stronger quenching of the perovskite PL when using TNRs as compared to mesoporous/compact TiO₂ thin films. Due to increased interfacial contact area between the ETL and perovskite with easier pore filling, charge separation efficiency is dramatically enhanced. Additionally, solid-state impedance spectroscopy results strongly suggested the suppression of interfacial charge recombination between TNRs and perovskite layer, compared to other ETLs. The optimal ETL morphology in this study was found to consist of an array of TNRs ∼300 nm in length and ∼40 nm in width. This work highlights the potential of TNR ETLs to achieve high performance solution-processed HPSCs.

Single crystal rutile titania nanowires grown by solvothermal synthesis are actively being researched for use as electron transporting scaffolds in perovskite solar cells, in low detection limit ultraviolet photodetectors, in photoelectrochemical water-splitting, and in chemiresistive and electrochemical sensing. The electron drift mobility (μ_n) in solution-grown TiO₂ nanowires is very low due to a high density of deep traps, and reduces performance in optoelectronic devices. In this study, the effects of molecular passivation of the nanowire surface by octadecylphosphonic acid (ODPA), on carrier transport in TiO₂ nanowire ensembles, were investigated using transient space charge limited current measurements. Infrared spectroscopy indicated the formation of a highly ordered phosphonate monolayer with a high likelihood of bidentate binding of ODPA to the rutile surface. We report the hole drift mobility (μ_p) for the first time in unpassivated solvothermal rutile nanowires to be 8.2 × 10⁻⁵ cm² V⁻¹ s⁻¹ and the use of ODPA passivation resulted in μ_p improving by nearly two orders of magnitude to 7.1 × 10⁻³ cm² V⁻¹ s⁻¹. Likewise, ODPA passivation produced between a 2 and 3 order of magnitude improvement in μ_n from ∼10⁻⁵–10⁻⁶ cm² V⁻¹ s⁻¹ to ∼10⁻³ cm² V⁻¹ s⁻¹. The bias dependence of the post-transit photocurrent decays in ODPA-passivated nanowires indicated that minority carriers were lost to trapping and/or monomolecular recombination for small values of bias (<5 V). Bimolecular recombination was indicated to be the dominant recombination mechanism at higher bias values.

GaAs was central to the development of quantum devices but is rarely used for nanowire-based quantum devices with InAs, InSb and SiGe instead taking the leading role. p-type GaAs nanowires offer a path to studying strongly confined 0D and 1D hole systems with strong spin–orbit effects, motivating our development of nanowire transistors featuring Be-doped p-type GaAs nanowires, AuBe alloy contacts and patterned local gate electrodes towards making nanowire-based quantum hole devices. We report on nanowire transistors with traditional substrate back-gates and EBL-defined metal/oxide top-gates produced using GaAs nanowires with three different Be-doping densities and various AuBe contact processing recipes. We show that contact annealing only brings small improvements for the moderately doped devices under conditions of lower anneal temperature and short anneal time. We only obtain good transistor performance for moderate doping, with conduction freezing out at low temperature for lowly doped nanowires and inability to reach a clear off-state under gating for the highly doped nanowires. Our best devices give on-state conductivity 95 nS, off-state conductivity 2 pS, on-off ratio $\sim {10}^{4}$, and sub-threshold slope 50 mV/dec at $T=4$ K. Lastly, we made a device featuring a moderately doped nanowire with annealed contacts and multiple top-gates. Top-gate sweeps show a plateau in the sub-threshold region that is reproducible in separate cool-downs and indicative of possible conductance quantisation highlighting the potential for future quantum device studies in this material system.

We report on the low-temperature fabrication of field-effect transistors by bridging pre-patterned electrodes using ZnO nanowires grown in situ, which operate without requiring post-growth processing or annealing. The devices show good performance using as-grown nanowires, with on–off ratios of 10⁵ and threshold voltages of 2 V. Electron microscopy shows the field-dependent nanowires hierarchically nucleate from larger ZnO nanorods, and both are oriented along a common c-axis. A high nanowire surface-to-volume ratio allows depleting electron traps on the nanowire surface to compensate intrinsic electron donors present throughout the nanowire bulk. This eliminates the need to reduce the electron concentration through high-temperature annealing, making the nanowires naturally field-dependent in their as-grown state.

Nanowire array ensembles contacted in a vertical geometry are extensively studied and considered strong candidates for next generations of industrial scale optoelectronics. Key challenges in this development deal with optimization of the doping profile of the nanowires and the interface between nanowires and transparent top contact. Here we report on photodetection characteristics associated with doping profile variations in InP nanowire array photodetectors. Bias-dependent tuning of the spectral shape of the responsivity is observed which is attributed to a Schottky-like contact at the nanowire–ITO interface. Angular dependent responsivity measurements, compared with simulated absorption spectra, support this conclusion. Furthermore, electrical simulations unravel the role of possible self-gating effects in the nanowires induced by the ITO/SiO_x wrap-gate geometry. Finally, we discuss possible reasons for the observed low saturation current at large forward biases.

Core–shell PbS/Sn:In₂O₃ and branched PbIn₂S₄/Sn:In₂O₃ nanowires have been obtained via the deposition of Pb over Sn:In₂O₃ nanowires and post growth processing under H₂S between 100 °C–200 °C and 300 °C–500 °C respectively. The PbS/Sn:In₂O₃ nanowires have diameters of 50–250 nm and consist of cubic PbS and In₂O₃ while the PbIn₂S₄/Sn:In₂O₃ nanowires consist of PbIn₂S₄ branches with diameters of 10–30 nm and an orthorhombic crystal structure. We discuss the growth mechanisms and also show that the density of electrons in the n-type Sn:In₂O₃ core is strongly dependent on the thickness of the p-type PbS shell, which must be smaller than 30 nm to prevent core depletion, via the self-consistent solution of the Poisson–Schrödinger equations in the effective mass approximation. The PbS/Sn:In₂O₃ and PbIn₂S₄/Sn:In₂O₃ nanowire networks had resistances of 100–200 Ω due to the large carrier densities and exhibited defect related photoluminescence at 2.2 eV and 1.5 eV respectively. We show that PbS in contact with polysulfide electrolyte has ohmic like behavior but the PbS/Sn:In₂O₃ nanowires gave, rectifying current voltage characteristics as a counter electrode in a quantum dot sensitized solar cell using a conventional ITO/TiO₂/CdS/CdSe photo anode, an open circuit voltage of ≈0.5 V, and short circuit current density of ≈1 mA cm⁻². In contrast the branched PbIn₂S₄/Sn:In₂O₃ nanowires exhibited a higher current carrying capability of ≈7 mA cm⁻² and higher power conversion efficiency of ≈2%.

The need for indium droplets to initiate self-catalyzed growth of InAs nanowires has been highly debated in the last few years. Here, we report on the use of indium droplets to tune the growth direction of self-catalyzed InAs nanowires. The indium droplets are formed in situ on InAs(Sb) stems. Their position is modified to promote growth in the 〈11–2〉 or equivalent directions. We also show that indium droplets can be used for the fabrication of InSb insertions in InAsSb nanowires. Our results demonstrate that indium droplets can initiate growth of InAs nanostructures as well as provide added flexibility to nanowire growth, enabling the formation of kinks and heterostructures, and offer a new approach in the growth of defect-free crystals.

Nanowire based solar cells have attracted great attention due to their potential for high efficiency and low device cost. Photovoltaic devices based on InP nanowires now have characteristics comparable to InP bulk solar cells. A detailed and direct correlation of the influence of growth conditions on performance is necessary to improve efficiency further. We explored the effects of the growth temperature, and of the addition of HCl during growth, on the efficiency of nanowire array based solar cell devices. By increasing HCl, the saturation dark current was reduced, and thereby the nanowire solar cell efficiency was enhanced from less than 1% to 7.6% under AM 1.5 illumination at 1 sun. At the same time, we observed that the solar cell efficiency decreased by increasing the tri-methyl-indium content, strongly suggesting that these effects are carbon related.