Lasing in Zn-doped GaAs nanowires on an iron film.

In this work, we demonstrate optically pumped lasing in highly Zn-doped GaAs nanowires (NWs) lying on an iron film. The conically shaped NWs are first covered with an 8 nm thick Al2O3film to prevent atmospheric oxidation and mitigate band-bending effects. Multimode and single-mode lasing have been observed for NWs with a length greater or smaller than 2µm, respectively. Finite difference time domain calculations reveal a weak electric field enhancement in the Al2O3layer at the NW/iron film interface for the lasing modes. The high Zn acceptor concentration in the NWs provides enhanced radiative efficiency and enables lasing on the iron film despite plasmonic losses. Our results open avenues for integrating NW lasers on ferromagnetic substrates to achieve new functionalities, such as magnetic field-induced modulation.

Dynamics and control of gold-encapped gallium arsenide nanowires imaged by 4D electron microscopy.

Eutectic-related reaction is a special chemical/physical reaction involving multiple phases, solid and liquid. Visualization of a phase reaction of composite nanomaterials with high spatial and temporal resolution provides a key understanding of alloy growth with important industrial applications. However, it has been a rather challenging task. Here, we report the direct imaging and control of the phase reaction dynamics of a single, as-grown free-standing gallium arsenide nanowire encapped with a gold nanoparticle, free from environmental confinement or disturbance, using four-dimensional (4D) electron microscopy. The nondestructive preparation of as-grown free-standing nanowires without supporting films allows us to study their anisotropic properties in their native environment with better statistical character. A laser heating pulse initiates the eutectic-related reaction at a temperature much lower than the melting points of the composite materials, followed by a precisely time-delayed electron pulse to visualize the irreversible transient states of nucleation, growth, and solidification of the complex. Combined with theoretical modeling, useful thermodynamic parameters of the newly formed alloy phases and their crystal structures could be determined. This technique of dynamical control aided by 4D imaging of phase reaction processes on the nanometer-ultrafast time scale opens new venues for engineering various reactions in a wide variety of other systems.

Four-Dimensional Probing of Phase-Reaction Dynamics in Au/GaAs Nanowires.

Nanoeutectic phase reaction covers the fundamental study of a chemical and physical reaction of multiple phases at the nanoscale. Here, we report the direct visualization of phase-reaction dynamics in Au/GaAs nanowires (NWs) using four-dimensional (4D) electron microscopy. The NW phase reactions were initiated with a pump laser pulse, while the following dynamics in the Au/GaAs NW was probed by a precisely time-delayed electron pulse. Single-pulse imaging reveals that the cubic zinc-blende NW presents a transient length increase within the time duration of ∼150 ns, giving the appearance of intermediate phase reactions at an early stage. A final length reduction of the NW is observed after the phase reactions have fully ended. In contrast, only length reduction is seen throughout the entire process in GaAs/AlGaAs core-shell and hexagonal wurtzite GaAs NWs. The reasons for the above intriguing phenomena are discussed. The eutectic-related phenomena in both zinc-blende and wurtzite materials offer a comprehensive understanding of phase-reaction dynamics in polytypic structures commonly available in compound semiconductors.

Optical Study of p-Doping in GaAs Nanowires for Low-Threshold and High-Yield Lasing.

Semiconductor nanowires suffer from significant non-radiative surface recombination; however, heavy p-type doping has proven to be a viable option to increase the radiative recombination rate and, hence, quantum efficiency of emission, allowing the demonstration of room-temperature lasing. Using a large-scale optical technique, we have studied Zn-doped GaAs nanowires to understand and quantify the effect of doping on growth and lasing properties. We measure the non-radiative recombination rate ( knr) to be (0.14 ± 0.04) ps-1 by modeling the internal quantum efficiency (IQE) as a function of doping level. By applying a correlative method, we identify doping and nanowire length as key controllable parameters determining lasing behavior, with reliable room-temperature lasing occurring for p ≳ 3 × 1018 cm-3 and lengths of ≳4 µm. We report a best-in-class core-only near-infrared nanowire lasing threshold of ∼10 µJ cm-2, and using a data-led filtering step, we present a method to simply identify subsets of nanowires with over 90% lasing yield.

Tailoring Second-Harmonic Emission from (111)-GaAs Nanoantennas.

Second-harmonic generation (SHG) in resonant dielectric Mie-scattering nanoparticles has been hailed as a powerful platform for nonlinear light sources. While bulk-SHG is suppressed in elemental semiconductors, for example, silicon and germanium due to their centrosymmetry, the group of zincblende III-V compound semiconductors, especially (100)-grown AlGaAs and GaAs, have recently been presented as promising alternatives. However, major obstacles to push the technology toward practical applications are the limited control over directionality of the SH emission and especially zero forward/backward radiation, resulting from the peculiar nature of the second-order nonlinear susceptibility of this otherwise highly promising group of semiconductors. Furthermore, the generated SH signal for (100)-GaAs nanoparticles depends strongly on the polarization of the pump. In this work, we provide both theoretically and experimentally a solution to these problems by presenting the first SHG nanoantennas made from (111)-GaAs embedded in a low index material. These nanoantennas show superior forward directionality compared to their (100)-counterparts. Most importantly, based on the special symmetry of the crystalline structure, it is possible to manipulate the SHG radiation pattern of the nanoantennas by changing the pump polarization without affecting the linear properties and the total nonlinear conversion efficiency, hence paving the way for efficient and flexible nonlinear beam-shaping devices.

The effect of Sn addition on GaAs nanowire grown by vapor-liquid-solid growth mechanism.

Impurity addition is a crucial aspect for III-V nanowire growth. In this study, we demonstrated the effect of the Sn addition on GaAs nanowire growth by metal-organic chemical vapor deposition. With increasing the tetraethyltin flow rate, the nanowire axial growth was suppressed while the nanowire lateral growth was promoted, as well as planar defects were increased. Systematic electron microscopy characterizations suggested that the Sn addition tuned the catalyst composition, changed the vapor-solid-liquid surfaces energies and hindered the Ga atoms diffusion on nanowire sidewalls, which is responsible for the observed changes in morphology and structural quality of grown GaAs nanowires. This study contributes to understanding the role of impurity dopants on III-V nanowires growth, which will be of benefit for the design and fabrication of future nanowire-based devices.

Photoelectrochemical studies of InGaN/GaN MQW photoanodes.

The research interest in photoelectrochemical (PEC) water splitting is ever growing due to its potential to contribute towards clean and portable energy. However, the lack of low energy band gap materials with high photocorrosion resistance is the primary setback inhibiting this technology from commercialisation. The ternary alloy InGaN shows promise to meet the photoelectrode material requirements due to its high chemical stability and band gap tunability. The band gap of InGaN can be modulated from the UV to IR regions by adjusting the In concentration so as to absorb the maximum portion of the solar spectrum. This paper reports on the influence of In concentration on the PEC properties of planar and nanopillar (NP) InGaN/GaN multi-quantum well (MQW) photoanodes, where NPs were fabricated using a top-down approach. Results show that changing the In concentration, while having a minor effect on the PEC performance of planar MQWs, has an enormous impact on the PEC performance of NP MQWs, with large variations in the photocurrent density observed. Planar photoanodes containing MQWs generate marginally lower photocurrents compared to photoanodes without MQWs when illuminated with sunlight. NP MQWs with 30% In generated the highest photocurrent density of 1.6 mA cm-2, 4 times greater than that of its planar counterpart and 1.8 times greater than that of the NP photoanode with no MQWs. The InGaN/GaN MQWs also slightly influenced the onset potential of both the planar and NP photoanodes. Micro-photoluminescence, diffuse reflectance spectroscopy and IPCE measurements are used to explain these results.

Improved photoelectrochemical performance of GaN nanopillar photoanodes.

In this work, we report on the photoelectrochemical (PEC) investigation of n-GaN nanopillar (NP) photoanodes fabricated using metal organic chemical vapour deposition and the top-down approach. Substantial improvement in photocurrents is observed for GaN NP photoanodes compared to their planar counterparts. The role of carrier concentration and NP dimensions on the PEC performance of NP photoanodes is further elucidated. Photocurrent density is almost doubled for doped NP photoanodes whereas no improvement is noticed for undoped NP photoanodes. While the diameter of GaN NP is found to influence the onset potential, carrier concentration is found to affect both the onset and overpotential of the electrodes. Optical and electrochemical impedance spectroscopy characterisations are utilised to further explain the PEC results of NP photoanodes. Finally, improvement in the photostability of NP photoanodes with the addition of NiO as a co-catalyst is investigated.

Radiation effects on GaAs/AlGaAs core/shell ensemble nanowires and nanowire infrared photodetectors.

With the recent advances in nanowire (NW) growth and fabrication, there has been rapid development and application of GaAs NWs in optoelectronics. It is also of importance to study the radiation tolerance of optoelectronic nano-devices for atomic energy and space-based applications. Here, photoluminescence (PL) and time-resolved photoluminescence measurements were carried out on GaAs/AlGaAs core/shell NWs at room temperature before and after 1 MeV proton irradiation with fluences ranging from 1.0 × 1012-3.0 × 1013 cm-2. It is found that the GaAs/AlGaAs core/shell NWs with smaller diameter show much less PL degradation compared with the ones with larger diameters. The increased radiation hardness is mainly attributed to the improvement of a room temperature dynamic-annealing mechanism near the surface of the NWs. We also found that the minority carrier lifetime is closely related to both the PL intensity and defect density induced by irradiation. Finally, GaAs/AlGaAs ensemble NW photodetectors operating in the near-infrared spectral regime have been demonstrated. The influence of proton irradiation on light and dark current characteristics also indicates that NW structures are a good potential candidate for radiation harsh-environment applications.

Nanowire Array Breath Acetone Sensor for Diabetes Monitoring.

Diabetic ketoacidosis (DKA) is a life-threatening acute complication of diabetes characterized by the accumulation of ketone bodies in the blood. Breath acetone, a ketone, directly correlates with blood ketones. Therefore, monitoring breath acetone can significantly enhance the safety and efficacy of diabetes care. In this work, the design and fabrication of an InP/Pt/chitosan nanowire array-based chemiresistive acetone sensor is reported. By incorporation of chitosan as a surface-functional layer and a Pt Schottky contact for efficient charge transfer processes and photovoltaic effect, self-powered, highly selective acetone sensing is achieved. The sensor has exhibited an ultra-wide acetone detection range from sub-ppb to >100 000 ppm level at room temperature, covering those in the exhaled breath from healthy individuals (300-800 ppb) to people at high risk of DKA (>75 ppm). The nanowire sensor has also been successfully integrated into a handheld breath testing prototype, the Ketowhistle, which can successfully detect different ranges of acetone concentrations in simulated breath samples. The Ketowhistle demonstrates the immediate potential for non-invasive ketone monitoring for people living with diabetes, in particular for DKA prevention.

Core-shell GaN/AlGaN nanowires grown by selective area epitaxy.

GaN/AlGaN core-shell nanowires with various Al compositions have been grown on GaN nanowire array using selective area metal organic chemical vapor deposition technique. Growth of the AlGaN shell using pure N2 carrier gas resulted in a smooth surface for the nonpolar m-plane sidewalls with superior optical properties, whereas, growth using a mixed N2/H2 carrier gas resulted in a striated surface similar to the commonly observed morphology in the growth of nonpolar III-nitrides. The Al compositions in the AlGaN shells are found to be less than the gas phase input ratio. The systematic reduction in efficiency of Al incorporation in the AlGaN shells with increasing the Al molar flow in the gas phase is attributed to geometric loss, strain-limited Al incorporation, and increased gas phase parasitic reactions. Defect-related luminescence has been observed for AlGaN shells with Al content ≥ 30% and the origin of the defect luminescence has been determined as the (VIII-2ON)1- complex. Microstructural analysis of the AlGaN shells revealed that the dominant defects are partial dislocations. Growth of the nonpolar m-plane AlxGa1-xN/AlyGa1-yN quantum wells on the sidewalls of the GaN nanowires produced arrays with excellent morphology and optical emission, which demonstrated the viability of such a growth scheme for large area efficient ultraviolet LEDs as well as for next generation ultraviolet micro-LEDs.

A Self-Powered Portable Nanowire Array Gas Sensor for Dynamic NO2 Monitoring at Room Temperature.

The fast development of the Internet of Things (IoT) has driven an increasing consumer demand for self-powered gas sensors for real-time data collection and autonomous responses in industries such as environmental monitoring, workplace safety, smart cities, and personal healthcare. Despite intensive research and rapid progress in the field, most reported self-powered devices, specifically NO2 sensors for air pollution monitoring, have limited sensitivity, selectivity, and scalability. Here, a novel photovoltaic self-powered NO2 sensor is demonstrated based on axial p-i-n homojunction InP nanowire (NW) arrays, that overcome these limitations. The optimized innovative InP NW array device is designed by numerical simulation for insights into sensing mechanisms and performance enhancement. Without a power source, this InP NW sensor achieves an 84% sensing response to 1 ppm NO2 and records a limit of detection down to the sub-ppb level, with little dependence on the incident light intensity, even under <5% of 1 sun illumination. Based on this great environmental fidelity, the sensor is integrated into a commercial microchip interface to evaluate its performance in the context of dynamic environmental monitoring of motor vehicle exhaust. The results show that compound semiconductor nanowires can form promising self-powered sensing platforms suitable for future mega-scale IoT systems.

Effect of Au substrate and coating on the lasing characteristics of GaAs nanowires.

Optically pumped lasing from highly Zn-doped GaAs nanowires lying on an Au film substrate and from Au-coated nanowires has been demonstrated up to room temperature. The conically shaped GaAs nanowires were first coated with a 5 nm thick Al2O3 shell to suppress atmospheric oxidation and band-bending effects. Doping with a high Zn concentration increases both the radiative efficiency and the material gain and leads to lasing up to room temperature. A detailed analysis of the observed lasing behavior, using finite-difference time domain simulations, reveals that the lasing occurs from low loss hybrid modes with predominately photonic character combined with electric field enhancement effects. Achieving low loss lasing from NWs on an Au film and from Au coated nanowires opens new prospects for on-chip integration of nanolasers with new functionalities including electro-optical modulation, conductive shielding, and polarization control.

Forward and Backward Switching of Nonlinear Unidirectional Emission from GaAs Nanoantennas.

High-index III-V semiconductor nanoantennas have gained great attention for enhanced nonlinear light-matter interactions, in the past few years. However, the complexity of nonlinear emission profiles imposes severe constraints on practical applications, such as in optical communications and integrated optoelectronic devices. These complexities include the lack of unidirectional nonlinear emission and the severe challenges in switching between forward and backward emissions, due to the structure of the susceptibility tensor of the III-V nanoantennas. Here, we propose a solution to both issues via engineering the nonlinear tensor of the nanoantennas. The special nonlinear tensorial properties of zinc-blende material can be used to engineer the nonlinear characteristics via growing the nanoantennas along different crystalline orientations. Based on the nonlinear multipolar effect, we have designed and fabricated (110)-grown GaAs nanoantennas, with engineered tensorial properties, embedded in a transparent low-index material. Our technique provides an approach not only for unidirectional second-harmonic generation (SHG) forward or backward emission but also for switching from one to another. Importantly, switching the SHG emission directionality is obtained only by rotating the polarization of the incident light, without the need for physical variation of the antennas or the environment. This characteristic is an advantage, as compared to other nonlinear nanoantennas, including (100)- and (111)-grown III-V counterparts or silicon and germanium nanoantennas. Indeed, (110)-GaAs nanoantennas allow for engineering the nonlinear nanophotonic systems including nonlinear "Huygens metasurfaces" and offer exciting opportunities for various nonlinear nanophotonics technologies, such as nanoscale light routing and light sources, as well as multifunctional flat optical elements.

Threshold reduction and yield improvement of semiconductor nanowire lasers via processing-related end-facet optimization.

Both gain medium design and cavity geometry are known to be important for low threshold operation of semiconductor nanowire lasers. For many applications nanowire lasers need to be transferred from the growth substrate to a low-index substrate; however, the impact of the transfer process on optoelectronic performance has not been studied. Ultrasound, PDMS-assisted and mechanical rubbing are the most commonly used methods for nanowire transfer; each method may cause changes in the fracture point of the nanowire which can potentially affect both length and end-face mirror quality. Here we report on four common approaches for nanowire transfer. Our results show that brief ultrasound and PDMS-assisted transfer lead to optimized optoelectronic performance, as confirmed by ensemble median lasing threshold values of 98 and 104 µJ cm-2 respectively, with nanowires transferred by ultrasound giving a high lasing yield of 72%. The mean threshold difference between samples is shown to be statistically significant: while a significant difference in mean length from different transfer methods is seen, it is shown by SEM that end-facet quality is also affected and plays an important role on threshold gain for this nanowire architecture.

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.