Cathodoluminescence visualisation of local thickness variations of GaAs/AlGaAs quantum-well tubes on nanowires.

We present spatially and spectrally resolved emission from nanowires with a thin radial layer of GaAs embedded in AlGaAs barriers, grown radially around taper-free GaAs cores. The GaAs layers are thin enough to show quantization, and are quantum wells. Due to their shape, they are referred to as quantum well tubes (QWTs). We have investigated three different nominal QWT thicknesses: 1.5, 2.0, and 6.0 nm. They all show average emission spectra from the QWT with an energy spread corresponding to a thickness variation of ±30%. We observe no thickness gradient along the length of the nanowires. Individual NWs show a number of peaks, corresponding to different QW thicknesses. Apart from the thinnest QWT, the integrated emission from the QWTs shows homogeneous emission intensity along the NW. The thinnest QWTs show patchy emission patterns due to the incomplete coverage of the QWT. We observe a few NWs with larger diameters. The QWTs in these NWs show spatially resolved variations across the NW. An increase in the local thickness of the QWT at the corners blocks the diffusion of carriers from facet to facet, thereby enabling us to visualise the thickness variations of the radial quantum wells.

Multiwavelength Single Nanowire InGaAs/InP Quantum Well Light-Emitting Diodes.

We report multiwavelength single InGaAs/InP quantum well nanowire light-emitting diodes grown by metal organic chemical vapor deposition using selective area epitaxy technique and reveal the complex origins of their electroluminescence properties. We observe that the single InGaAs/InP quantum well embedded in the nanowire consists of three components with different chemical compositions, axial quantum well, ring quantum well, and radial quantum well, leading to the electroluminescence emission with multiple wavelengths. The electroluminescence measurements show a strong dependence on current injection levels as well as temperatures and these are explained by interpreting the equivalent circuits in a minimized area of the device. It is also found that the electroluminescence properties are closely related to the distinctive triangular morphology with an inclined facet of the quantum well nanowire. Our study provides important new insights for further design, growth, and fabrication of high-performance quantum well-based nanowire light sources for a wide range of future optoelectronic and photonic applications.

Simultaneous Selective-Area and Vapor-Liquid-Solid Growth of InP Nanowire Arrays.

Selective-area epitaxy is highly successful in producing application-ready size-homogeneous arrays of III-V nanowires without the need to use metal catalysts. Previous works have demonstrated excellent control of nanowire properties but the growth mechanisms remain rather unclear. Herein, we report a detailed growth study revealing that fundamental growth mechanisms of pure wurtzite InP ⟨111⟩A nanowires can indeed differ significantly from the simple picture of a facet-limited selective-area growth process. A dual growth regime with and without metallic droplet is found to coexist under the same growth conditions for different diameter nanowires. Incubation times and highly nonmonotonous growth rate behaviors are revealed and explained within a dedicated kinetic model.

In(x)Ga(1-x)As nanowires with uniform composition, pure wurtzite crystal phase and taper-free morphology.

Obtaining compositional homogeneity without compromising morphological or structural quality is one of the biggest challenges in growing ternary alloy compound semiconductor nanowires. Here we report growth of Au-seeded InxGa1-xAs nanowires via metal-organic vapour phase epitaxy with uniform composition, morphology and pure wurtzite (WZ) crystal phase by carefully optimizing growth temperature and V/III ratio. We find that high growth temperatures allow the InxGa1-xAs composition to be more uniform by suppressing the formation of typically observed spontaneous In-rich shells. A low V/III ratio results in the growth of pure WZ phase InxGa1-xAs nanowires with uniform composition and morphology while a high V/III ratio allows pure zinc-blende (ZB) phase to form. Ga incorporation is found to be dependent on the crystal phase favouring higher Ga concentration in ZB phase compared to the WZ phase. Tapering is also found to be more prominent in defective nanowires hence it is critical to maintain the highest crystal structure purity in order to minimize tapering and inhomogeneity. The InP capped pure WZ In0.65Ga0.35As core-shell nanowire heterostructures show 1.54 µm photoluminescence, close to the technologically important optical fibre telecommunication wavelength, which is promising for application in photodetectors and nanoscale lasers.

Understanding the true shape of Au-catalyzed GaAs nanowires.

With increasing interest in nanowire-based devices, a thorough understanding of the nanowire shape is required to gain tight control of the quality of nanowire heterostructures and improve the performance of related devices. We present a systematic study of the sidewalls of Au-catalyzed GaAs nanowires by investigating the faceting process from the beginning with vapor-liquid-solid (VLS) nucleation, followed by the simultaneous radial growth on the sidewalls, and to the end with sidewall transformation during annealing. The VLS nucleation interface of our GaAs nanowires is revealed by examining cross sections of the nanowire, where the nanowire exhibits a Reuleaux triangular shape with three curved surfaces along {112}A. These curved surfaces are not thermodynamically stable and adopt {112}A facets during radial growth. We observe clear differences in radial growth rate between the ⟨112⟩A and ⟨112⟩B directions with {112}B facets forming due to the slower radial growth rate along ⟨112⟩B directions. These sidewalls transform to {110} facets after high temperature (>500 °C) annealing. A nucleation model is proposed to explain the origin of the Reuleaux triangular shape of the nanowires, and the sidewall evolution is explained by surface kinetic and thermodynamic limitations.

Selective-area epitaxy of pure wurtzite InP nanowires: high quantum efficiency and room-temperature lasing.

We report the growth of stacking-fault-free and taper-free wurtzite InP nanowires with diameters ranging from 80 to 600 nm using selective-area metal-organic vapor-phase epitaxy and experimentally determine a quantum efficiency of ∼50%, which is on par with InP epilayers. We also demonstrate room-temperature, photonic mode lasing from these nanowires. Their excellent structural and optical quality opens up new possibilities for both fundamental quantum optics and optoelectronic devices.

Electron-pinned defect-dipoles for high-performance colossal permittivity materials.

The immense potential of colossal permittivity (CP) materials for use in modern microelectronics as well as for high-energy-density storage applications has propelled much recent research and development. Despite the discovery of several new classes of CP materials, the development of such materials with the required high performance is still a highly challenging task. Here, we propose a new electron-pinned, defect-dipole route to ideal CP behaviour, where hopping electrons are localized by designated lattice defect states to generate giant defect-dipoles and result in high-performance CP materials. We present a concrete example, (Nb+In) co-doped TiO2 rutile, that exhibits a largely temperature- and frequency-independent colossal permittivity (> 10(4)) as well as a low dielectric loss (mostly < 0.05) over a very broad temperature range from 80 to 450 K. A systematic defect analysis coupled with density functional theory modelling suggests that 'triangular' In2(3+)Vo(••)Ti(3+) and 'diamond' shaped Nb2(5+)Ti(3+)A(Ti) (A = Ti(3+)/In(3+)/Ti(4+)) defect complexes are strongly correlated, giving rise to large defect-dipole clusters containing highly localized electrons that are together responsible for the excellent CP properties observed in co-doped TiO2. This combined experimental and theoretical work opens up a promising feasible route to the systematic development of new high-performance CP materials via defect engineering.

Polarity-driven 3-fold symmetry of GaAs/AlGaAs core multishell nanowires.

AlGaAs/GaAs quantum well heterostructures based on core-multishell nanowires exhibit excellent optical properties which are acutely sensitive to structure and morphology. We characterize these heterostructures and observe them to have 3-fold symmetry about the nanowire axis. Using aberration-corrected annular dark field scanning transmission electron microscopy (ADF-STEM), we measure directly the polarity of the crystal structure and correlate this with the shape and facet orientation of the GaAs core, quantum wells and cap, and the width of radial Al-rich bands. We discuss how the underlying polarity of the crystal structure drives the growth of these heterostructures with a 3-fold symmetry resulting in a nonuniform GaAs quantum well tube and AlGaAs shell. These observations suggest that the AlGaAs growth rate is faster along the [112] B compared to the [112] A directions and/or that there is a polarity driven surface reconstruction generating AlGaAs growth fronts inclined to the {110} planes. In contrast, the observations suggest that the opposite is true for the GaAs growth, with the preferred surface reconstruction plane being parallel to {110} and an apparent faster growth rate along the [112] A. This two-dimensional layer growth of the nanowire multishells strongly depends on the surface energies and surface reconstruction of the facets which are related to the crystal polarity and lead to the 3-fold symmetry observed here.

Direct observation of charge-carrier heating at WZ-ZB InP nanowire heterojunctions.

We have investigated the dynamics of hot charge carriers in InP nanowire ensembles containing a range of densities of zinc-blende inclusions along the otherwise wurtzite nanowires. From time-dependent photoluminescence spectra, we extract the temperature of the charge carriers as a function of time after nonresonant excitation. We find that charge-carrier temperature initially decreases rapidly with time in accordance with efficient heat transfer to lattice vibrations. However, cooling rates are subsequently slowed and are significantly lower for nanowires containing a higher density of stacking faults. We conclude that the transfer of charges across the type II interface is followed by release of additional energy to the lattice, which raises the phonon bath temperature above equilibrium and impedes the carrier cooling occurring through interaction with such phonons. These results demonstrate that type II heterointerfaces in semiconductor nanowires can sustain a hot charge-carrier distribution over an extended time period. In photovoltaic applications, such heterointerfaces may hence both reduce recombination rates and limit energy losses by allowing hot-carrier harvesting.

Polarization tunable, multicolor emission from core-shell photonic III-V semiconductor nanowires.

We demonstrate luminescence from both the core and the shell of III-V semiconductor photonic nanowires by coupling them to plasmonic silver nanoparticles. This demonstration paves the way for increasing the quantum efficiency of large surface area nanowire light emitters. The relative emission intensity from the core and the shell is tuned by varying the polarization of the excitation source since their polarization response can be independently controlled. Independent control on emission wavelength and polarization dependence of emission from core-shell nanowire heterostructures opens up opportunities that have not yet been imagined for nanoscale polarization sensitive, wavelength-selective, or multicolor photonic devices based on single nanowires or nanowire arrays.

Ultralow surface recombination velocity in InP nanowires probed by terahertz spectroscopy.

Using transient terahertz photoconductivity measurements, we have made noncontact, room temperature measurements of the ultrafast charge carrier dynamics in InP nanowires. InP nanowires exhibited a very long photoconductivity lifetime of over 1 ns, and carrier lifetimes were remarkably insensitive to surface states despite the large nanowire surface area-to-volume ratio. An exceptionally low surface recombination velocity (170 cm/s) was recorded at room temperature. These results suggest that InP nanowires are prime candidates for optoelectronic devices, particularly photovoltaic devices, without the need for surface passivation. We found that the carrier mobility is not limited by nanowire diameter but is strongly limited by the presence of planar crystallographic defects such as stacking faults in these predominantly wurtzite nanowires. These findings show the great potential of very narrow InP nanowires for electronic devices but indicate that improvements in the crystallographic uniformity of InP nanowires will be critical for future nanowire device engineering.

InAs nanowire arrays for room-temperature ultra-broadband infrared photodetection.

Detection of short-wave infrared (SWIR) and mid-wave infrared (MWIR) emissions remains challenging despite their importance in many emerging applications, including night vision, space imaging and remote sensing. III-V compound semiconductor materials such as InAs have an ideal band gap covering a spectral regime from near-infrared (NIR), SWIR to MWIR. However, due to their high dark current, InAs photodetectors normally require a low-temperature operation, which has greatly limited their practical applications. Here, we report the engineering of InAs nanowire arrays to achieve efficient photodetection of light at wavelengths ranging from NIR to MWIR (3500 nm). By using selective area metal-organic vapour-phase epitaxy, we optimise the nanowire growth temperature and V/III ratio to achieve wurtzite (WZ)-based InAs nanowire arrays with a high WZ density of ∼67%. Due to the n-type background doping of the InAs nanowires and the p-type InAs substrate used for nanowire growth, a p-n junction is formed, and an ultrawide room-temperature photoresponse ranging from 500 to 3500 nm is obtained under zero bias. It is found that the waveguide modes supported by the InAs nanowires result in a high peak responsivity of 0.44 A W-1 and a detectivity of 1.25 × 1010 cm √Hz W-1 at a wavelength of 1600 nm, a bias voltage of only -0.1 V and a relatively high operating temperature of 150 K. Such a strong light trapping effect in the InAs nanowires also leads to significantly lower reflection compared to that observed in planar photodetectors, and thus strong absorption in the substrate extending the photoresponse up to the InAs bandgap edge of 3500 nm. Our work shows that through careful material optimisation and device design, InAs nanowire arrays are promising for the development of high-performance ultra-broadband infrared photodetectors for wavelengths ranging from NIR, SWIR to MWIR.

Growth of straight InAs-on-GaAs nanowire heterostructures.

One of the main motivations for the great interest in semiconductor nanowires is the possibility of easily growing advanced heterostructures that might be difficult or even impossible to achieve in thin films. For III-V semiconductor nanowires, axial heterostructures with an interchange of the group III element typically grow straight in only one interface direction. In the case of InAs-GaAs heterostructures, straight nanowire growth has been demonstrated for growth of GaAs on top of InAs, but so far never in the other direction. In this article, we demonstrate the growth of straight axial heterostructures of InAs on top of GaAs. The heterostructure interface is sharp and we observe a dependence on growth parameters closely related to crystal structure as well as a diameter dependence on straight nanowire growth. The results are discussed by means of accurate first principles calculations of the interfacial energies. In addition, the role of the gold seed particle, the effect of its composition at different stages during growth, and its size are discussed in relation to the results observed.

Phase perfection in zinc Blende and Wurtzite III-V nanowires using basic growth parameters.

Controlling the crystallographic phase purity of III-V nanowires is notoriously difficult, yet this is essential for future nanowire devices. Reported methods for controlling nanowire phase require dopant addition, or a restricted choice of nanowire diameter, and only rarely yield a pure phase. Here we demonstrate that phase-perfect nanowires, of arbitrary diameter, can be achieved simply by tailoring basic growth parameters: temperature and V/III ratio. Phase purity is achieved without sacrificing important specifications of diameter and dopant levels. Pure zinc blende nanowires, free of twin defects, were achieved using a low growth temperature coupled with a high V/III ratio. Conversely, a high growth temperature coupled with a low V/III ratio produced pure wurtzite nanowires free of stacking faults. We present a comprehensive nucleation model to explain the formation of these markedly different crystal phases under these growth conditions. Critical to achieving phase purity are changes in surface energy of the nanowire side facets, which in turn are controlled by the basic growth parameters of temperature and V/III ratio. This ability to tune crystal structure between twin-free zinc blende and stacking-fault-free wurtzite not only will enhance the performance of nanowire devices but also opens new possibilities for engineering nanowire devices, without restrictions on nanowire diameters or doping.

Understanding the role of facets and twin defects in the optical performance of GaAs nanowires for laser applications.

GaAs nanowires are regarded as promising building blocks of future optoelectronic devices. Despite progress, the growth of high optical quality GaAs nanowires is a standing challenge. Understanding the role of twin defects and nanowire facets on the optical emission and minority carrier lifetime of GaAs nanowires is key for the engineering of their optoelectronic properties. Here, we present new insights into the microstructural parameters controlling the optical properties of GaAs nanowires, grown via selective-area metal-organic vapor-phase epitaxy. We observe that these GaAs nanowires have a twinned zinc blende crystal structure with taper-free {110} side facets that result in an ultra-low surface recombination velocity of 3.5 × 104 cm s-1. This is an order of magnitude lower than that reported for defect-free GaAs nanowires grown by the vapor-liquid-solid technique. Using time-resolved photoluminescence and cathodoluminescence measurements, we untangle the local correlation between structural and optical properties demonstrating the superior role of the side facets in determining recombination rates over that played by twin defects. The low surface recombination velocity of these taper-free {110} side facets enable us to demonstrate, for the first time, low-temperature lasing from bare (unpassivated) GaAs nanowires, and also efficient room-temperature lasing after passivation with an AlGaAs shell.

Facet-Related Non-uniform Photoluminescence in Passivated GaAs Nanowires.

The semiconductor nanowire architecture provides opportunities for non-planar electronics and optoelectronics arising from its unique geometry. This structure gives rise to a large surface area-to-volume ratio and therefore understanding the effect of nanowire surfaces on nanowire optoelectronic properties is necessary for engineering related devices. We present a systematic study of the non-uniform optical properties of Au-catalyzed GaAs/AlGaAs core-shell nanowires introduced by changes in the sidewall faceting. Significant variation in intra-wire photoluminescence (PL) intensity and PL lifetime (τ PL ) was observed along the nanowire axis, which was strongly correlated with the variation of sidewall facets from {112} to {110} from base to tip. Faster recombination occurred in the vicinity of {112}-oriented GaAs/AlGaAs interfaces. An alternative nanowire heterostructure, the radial quantum well tube consisting of a GaAs layer sandwiched between two AlGaAs barrier layers, is proposed and demonstrates superior uniformity of PL emission along the entire length of nanowires. The results emphasize the significance of nanowire facets and provide important insights for nanowire device design.

Engineering III-V Semiconductor Nanowires for Device Applications.

III-V semiconductor nanowires offer potential new device applications because of the unique properties associated with their 1D geometry and the ability to create quantum wells and other heterostructures with a radial and an axial geometry. Here, an overview of challenges in the bottom-up approaches for nanowire synthesis using catalyst and catalyst-free methods and the growth of axial and radial heterostructures is given. The work on nanowire devices such as lasers, light emitting nanowires, and solar cells and an overview of the top-down approaches for water splitting technologies is reviewed. The authors conclude with an analysis of the research field and the future research directions.

Ultrathin Ta2O5 electron-selective contacts for high efficiency InP solar cells.

Heterojunction solar cells with transition-metal-oxide-based carrier-selective contacts have been gaining considerable research interest owing to their amenability to low-cost fabrication methods and elimination of parasitic absorption and complex semiconductor doping process. In this work, we propose tantalum oxide (Ta2O5) as a novel electron-selective contact layer for photo-generated carrier separation in InP solar cells. We confirm the electron-selective properties of Ta2O5 by investigating band energetics at the InP-Ta2O5 interface using X-ray photoelectron spectroscopy. Time-resolved photoluminescence and power dependent photoluminescence reveal that the Ta2O5 inter-layer also mitigates parasitic recombination at the InP/transparent conducting oxide interface. With an 8 nm Ta2O5 layer deposited using an atomic layer deposition (ALD) system, we demonstrate a planar InP solar cell with an open circuit voltage, Voc, of 822 mV, a short circuit current density, Jsc, of 30.1 mA cm-2, and a fill factor of 0.77, resulting in an overall device efficiency of 19.1%. The Voc is the highest reported value to date for an InP heterojunction solar cells with carrier-selective contacts. The proposed Ta2O5 material may be of interest not only for other solar cell architectures including perovskite cells and organic solar cells, but also across a wide range of optoelectronics applications including solid state emitting devices, photonic crystals, planar light wave circuits etc.

InGaAsP as a Promising Narrow Band Gap Semiconductor for Photoelectrochemical Water Splitting.

While photoelectrochemical (PEC) water splitting is a very promising route toward zero-carbon energy, conversion efficiency remains limited. Semiconductors with narrower band gaps can absorb a much greater portion of the solar spectrum, thereby increasing efficiency. However, narrow band gap (∼1 eV) III-V semiconductor photoelectrodes have not yet been thoroughly investigated. In this study, the narrow band gap quaternary III-V alloy InGaAsP is demonstrated for the first time to have great potential for PEC water splitting, with the long-term goal of developing high-efficiency tandem PEC devices. TiO2-coated InGaAsP photocathodes generate a photocurrent density of over 30 mA/cm2 with an onset potential of 0.45 V versus reversible hydrogen electrode, yielding an applied bias efficiency of over 7%. This is an excellent performance, given that nearly all power losses can be attributed to reflection losses. X-ray photoelectron spectroscopy and photoluminescence spectroscopy show that InGaAsP and TiO2 form a type-II band alignment, greatly enhancing carrier separation and reducing recombination losses. Beyond water splitting, the tunable band gap of InGaAsP could be of further interest in other areas of photocatalysis, including CO2 reduction.