Heterometallic lanthanide complexes with site-specific binding that enable simultaneous visible and NIR-emission.

Macrocyclic lanthanide complexes have become widely developed due to their distinctive luminescence characteristics and wide range of applications in biological imaging. However, systems with sufficient brightness and metal selectivity can be difficult to produce on a molecular scale. Presented herein is the stepwise introduction of differing lanthanide ions in a bis-DO3A/DTPA scaffold to afford three trinuclear bimetallic [Ln2Ln'] lanthanide complexes with site-specific, controlled binding [(Yb2Tb), (Eu2Tb), (Yb2Eu)]. The complexes display simultaneous emission from all LnIII centers across the visible (TbIII, EuIII) and near infra-red (YbIII) spectrum when excited via phenyl ligand sensitization at a wide range of temperatures and are consequently of interest for exploiting imaging in the near infra-red II biological window. Analysis of lifetime data over a range of excitation regimes reveals intermetallic communication between TbIII and EuIII centers and further develops the understanding of multimetallic lanthanide complexes.

Bottom-up, Chip-Scale Engineering of Low Threshold, Multi-Quantum-Well Microring Lasers.

Integrated, on-chip lasers are vital building blocks in future optoelectronic and nanophotonic circuitry. Specifically, III-V materials that are of technological relevance have attracted considerable attention. However, traditional microcavity laser fabrication techniques, including top-down etching and bottom-up catalytic growth, often result in undesirable cavity geometries with poor scalability and reproducibility. Here, we utilize the selective area epitaxy method to deterministically engineer thousands of microring lasers on a single chip. Specifically, we realize a catalyst-free, epitaxial growth of a technologically critical material, InAsP/InP, in a ring-like cavity with embedded multi-quantum-well heterostructures. We elucidate a detailed growth mechanism and leverage the capability to deterministically control the adatom diffusion lengths on selected crystal facets to reproducibly achieve ultrasmooth cavity sidewalls. The engineered devices exhibit a tunable emission wavelength in the telecommunication O-band and show low-threshold lasing with over 80% device efficacy across the chip. Our work marks a significant milestone toward the implementation of a fully integrated III-V materials platform for next-generation high-density integrated photonic and optoelectronic circuits.

Sub-Picosecond Carrier Dynamics Explored using Automated High-Throughput Studies of Doping Inhomogeneity within a Bayesian Framework.

Bottom-up production of semiconductor nanomaterials is often accompanied by inhomogeneity resulting in a spread in electronic properties which may be influenced by the nanoparticle geometry, crystal quality, stoichiometry, or doping. Using photoluminescence spectroscopy of a population of more than 11 000 individual zinc-doped gallium arsenide nanowires, inhomogeneity is revealed in, and correlation between doping and nanowire diameter by use of a Bayesian statistical approach. Recombination of hot-carriers is shown to be responsible for the photoluminescence lineshape; by exploiting lifetime variation across the population, hot-carrier dynamics is revealed at the sub-picosecond timescale showing interband electronic dynamics. High-throughput spectroscopy together with a Bayesian approach are shown to provide unique insight in an inhomogeneous nanomaterial population, and can reveal electronic dynamics otherwise requiring complex pump-probe experiments in highly non-equilibrium conditions.

Improving Quantum Well Tube Homogeneity Using Strained Nanowire Heterostructures.

Bottom-up grown nanostructures often suffer from significant dimensional inhomogeneity, and for quantum confined heterostructures, this can lead to a corresponding large variation in electronic properties. A high-throughput characterization methodology is applied to >15,000 nanoskived sections of highly strained GaAsP/GaAs radial core/shell quantum well heterostructures revealing high emission uniformity. While scanning electron microscopy shows a wide nanowire diameter spread of 540-60+60 nm, photoluminescence reveals a tightly bounded band-to-band transition energy of 1546-3+4 meV. A highly strained core/shell nanowire design is shown to reduce the dependence of emission on the quantum well width variation significantly more than in the unstrained case.

Holistic Determination of Optoelectronic Properties using High-Throughput Spectroscopy of Surface-Guided CsPbBr3 Nanowires.

Optoelectronic micro- and nanostructures have a vast parameter space to explore for modification and optimization of their functional performance. This paper reports on a data-led approach using high-throughput single nanostructure spectroscopy to probe >8000 structures, allowing for holistic analysis of multiple material and optoelectronic parameters with statistical confidence. The methodology is applied to surface-guided CsPbBr3 nanowires, which have complex and interrelated geometric, structural, and electronic properties. Photoluminescence-based measurements, studying both the surface and embedded interfaces, exploits the natural inter nanowire geometric variation to show that increasing the nanowire width reduces the optical bandgap, increases the recombination rate in the nanowire bulk, and reduces the rate at the surface interface. A model of carrier recombination and diffusion ascribes these trends to carrier density and strain effects at the interfaces and self-consistently retrieves values for carrier mobility, trap densities, bandgap, diffusion length, and internal quantum efficiency. The model predicts parameter trends, such as the variation of internal quantum efficiency with width, which is confirmed by experimental verification. As this approach requires minimal a priori information, it is widely applicable to nano- and microscale materials.

Adolescent Gender Dysphoria and the Informed Consent Model of Care.

The informed consent model of care for people who identify as transgender is predicated on the idea that a careful mental health assessment and a formal diagnosis of gender dysphoria are not necessary preconditions before starting a person on cross-sex hormones. This article considers the legality of the informed consent model in relation to adolescents under 18 in Australia in the light of the decisions of the Family Court in Re Kelvin (2017) 327 FLR 15; [2017] FamCAFC 258 (Re Kelvin) and Re Imogen (No 6) (2020) 61 Fam LR 344; [2020] FamCA 761. The approach taken by the Family Court is predicated on the treatment being a response to a clinically diagnosed disorder, diagnosed after proper assessment. Re Kelvin indicates that assessment and treatment should be conducted by a multidisciplinary team in accordance with internationally recognised standards and guidelines. For these reasons, practising under an informed consent model of care without a mental health assessment or working within a multidisciplinary team, is unlawful.

Self-Catalyzed AlGaAs Nanowires and AlGaAs/GaAs Nanowire-Quantum Dots on Si Substrates.

Self-catalyzed AlGaAs nanowires (NWs) and NWs with a GaAs quantum dot (QD) were monolithically grown on Si(111) substrates via solid-source molecular beam epitaxy. This growth technique is advantageous in comparison to the previously employed Au-catalyzed approach, as it removes Au contamination issues and renders the structures compatible with complementary metal-oxide-semiconductor (CMOS) technology applications. Structural studies reveal the self-formation of an Al-rich AlGaAs shell, thicker at the NW base and thinning towards the tip, with the opposite behavior observed for the NW core. Wide alloy fluctuations in the shell region are also noticed. AlGaAs NW structures with nominal Al contents of 10, 20, and 30% have strong room temperature photoluminescence, with emission in the range of 1.50-1.72 eV. Individual NWs with an embedded 4.9 nm-thick GaAs region exhibit clear QD behavior, with spatially localized emission, both exciton and biexciton recombination lines, and an exciton line width of 490 µeV at low temperature. Our results demonstrate the properties and behavior of the AlGaAs NWs and AlGaAs/GaAs NWQDs grown via the self-catalyzed approach for the first time and exhibit their potential for a range of novel applications, including nanolasers and single-photon sources.

Defect-Free Axially Stacked GaAs/GaAsP Nanowire Quantum Dots with Strong Carrier Confinement.

Axially stacked quantum dots (QDs) in nanowires (NWs) have important applications in nanoscale quantum devices and lasers. However, there is lack of study of defect-free growth and structure optimization using the Au-free growth mode. We report a detailed study of self-catalyzed GaAsP NWs containing defect-free axial GaAs QDs (NWQDs). Sharp interfaces (1.8-3.6 nm) allow closely stack QDs with very similar structural properties. High structural quality is maintained when up to 50 GaAs QDs are placed in a single NW. The QDs maintain an emission line width of <10 meV at 140 K (comparable to the best III-V QDs, including nitrides) after having been stored in an ambient atmosphere for over 6 months and exhibit deep carrier confinement (∼90 meV) and the largest reported exciton-biexciton splitting (∼11 meV) for non-nitride III-V NWQDs. Our study provides a solid foundation to build high-performance axially stacked NWQD devices that are compatible with CMOS technologies.

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.

Carrier dynamics and recombination mechanisms in InP twinning superlattice nanowires.

Nominal dopant-free zinc blende twinning superlattice InP nanowires have been grown with high crystal-quality and taper-free morphology. Here, we demonstrate its superior optical performance and clarify the different carrier recombination mechanisms at different temperatures using a time resolved photoluminescence study. The existence of regular twin planes and lateral overgrowth do not significantly increase the defect density. At room temperature, the as-grown InP nanowires have a strong emission at 1.348 eV and long minority carrier lifetime (∼3 ns). The carrier recombination dynamics is mainly dominated by nonradiative recombination due to surface trapping states; a wet chemical etch to reduce the surface trapping density thus boosts the emission intensity and increases the carrier lifetime to 7.1 ns. This nonradiative recombination mechanism dominates for temperatures above 155 K, and the carrier lifetime decreases with increasing temperature. However, radiative recombination dominates the carrier dynamics at temperature below ∼75 K, and a strong donor-bound exciton emission with a narrow emission linewidth of 4.5 meV is observed. Consequently, carrier lifetime increases with temperature. By revealing carrier recombination mechanisms over the temperature range 10-300 K, we demonstrate the attraction of using InP nanostructure for photonics and optoelectronic applications.

Heterostructure and Q-factor engineering for low-threshold and persistent nanowire lasing.

Continuous room temperature nanowire lasing from silicon-integrated optoelectronic elements requires careful optimisation of both the lasing cavity Q-factor and population inversion conditions. We apply time-gated optical interferometry to the lasing emission from high-quality GaAsP/GaAs quantum well nanowire laser structures, revealing high Q-factors of 1250 ± 90 corresponding to end-facet reflectivities of R = 0.73 ± 0.02. By using optimised direct-indirect band alignment in the active region, we demonstrate a well-refilling mechanism providing a quasi-four-level system leading to multi-nanosecond lasing and record low room temperature lasing thresholds (~6 µJ cm-2 pulse-1) for III-V nanowire lasers. Our findings demonstrate a highly promising new route towards continuously operating silicon-integrated nanolaser elements.

Characterization, Selection, and Microassembly of Nanowire Laser Systems.

Semiconductor nanowire (NW) lasers are a promising technology for the realization of coherent optical sources with ultrasmall footprint. To fully realize their potential in on-chip photonic systems, scalable methods are required for dealing with large populations of inhomogeneous devices that are typically randomly distributed on host substrates. In this work two complementary, high-throughput techniques are combined: the characterization of nanowire laser populations using automated optical microscopy, and a high-accuracy transfer-printing process with automatic device spatial registration and transfer. Here, a population of NW lasers is characterized, binned by threshold energy density, and subsequently printed in arrays onto a secondary substrate. Statistical analysis of the transferred and control devices shows that the transfer process does not incur measurable laser damage, and the threshold binning can be maintained. Analysis on the threshold and mode spectra of the device populations proves the potential for using NW lasers for integrated systems fabrication.

Fourteen-Year Trends in the Criminal Justice Response to Child Sexual Abuse Reports in New South Wales.

This study of attrition compares the prosecution of child sexual offenses reported while the complainant was still a child with those in which the report was delayed into adulthood; it also compares matters involving adult and young (under 18 years) suspects/defendants. It is based on an analysis of police and court administrative data in New South Wales, Australia over a 14-year period (2003-2016). Only one in five (21.6%) proceeded beyond the investigation stage. Criminal proceedings were more likely to commence when the alleged victim was 7-12 years old at the time of the incident, when the suspect was an adult and at least 10 years older than the victim, and also when the report to police was made when the victim was an adult. Just over half (55.5%) of the matters finalized in court resulted in a conviction. Cases in the higher courts were less likely to be dismissed and more likely to feature guilty pleas and convictions at trial than cases in the lower courts. The overall estimate is that only 12% of offenses reported to police resulted in a conviction, at a relatively stable rate over 14 years. These findings are consistent with those of comparable studies.

Highly Strained III-V-V Coaxial Nanowire Quantum Wells with Strong Carrier Confinement.

Coaxial quantum wells (QWs) are ideal candidates for nanowire (NW) lasers, providing strong carrier confinement and allowing close matching of the cavity mode and gain medium. We report a detailed structural and optical study and the observation of lasing for a mixed group-V GaAsP NW with GaAs QWs. This system offers a number of potential advantages in comparison to previously studied common group-V structures ( e. g., AlGaAs/GaAs) including highly strained binary GaAs QWs, the absence of a lower band gap core region, and deep carrier potential wells. Despite the large lattice mismatch (∼1.7%), it is possible to grow defect-free GaAs coaxial QWs with high optical quality. The large band gap difference results in strong carrier confinement, and the ability to apply a high degree of compressive strain to the GaAs QWs is also expected to be beneficial for laser performance. For a non-fully optimized structure containing three QWs, we achieve low-temperature lasing with a low external (internal) threshold of 20 (0.9) µJ/cm2/pulse. In addition, a very narrow lasing line width of ∼0.15 nm is observed. These results extend the NW laser structure to coaxial III-V-V QWs, which are highly suitable as the platform for NW emitters.

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.

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.

Graphene-silicon-on-insulator (GSOI) Schottky diode photodetectors.

Graphene-silicon (GS) Schottky junctions have been demonstrated as an efficient architecture for photodetection. However, the response speed of such devices for free space light detection has so far been limited to 10s-100s of kHz for wavelength λ >500 nm. Here, we demonstrate GS Schottky junction photodetectors fabricated on a silicon-on-insulator substrate (SOI) with response speeds approaching 1 GHz, attributed to the reduction of the photo-active silicon layer thickness to 10 µm and with it a suppression of speed-limiting diffusion currents. Graphene-silicon-on-insulator photodetectors (GSOI-PDs) exhibit a negligible influence of wavelength on response speed and only a modest compromise in responsivities compared to GS junctions fabricated on bulk silicon. Noise-equivalent-power (NEP) and specific detectivity (D*) of GSOI photodetectors are 14.5 pW and 7.83 × 1010 cm Hz1/2 W-1, respectively, in ambient conditions. We further demonstrate that combining GSOI-PDs with micro-optical elements formed by modifying the surface topography enables engineering of the spectral and angular response.

Towards substrate engineering of graphene-silicon Schottky diode photodetectors.

Graphene-silicon Schottky diode photodetectors possess beneficial properties such as high responsivities and detectivities, broad spectral wavelength operation and high operating speeds. Various routes and architectures have been employed in the past to fabricate devices. Devices are commonly based on the removal of the silicon-oxide layer on the surface of silicon by wet-etching before deposition of graphene on top of silicon to form the graphene-silicon Schottky junction. In this work, we systematically investigate the influence of the interfacial oxide layer, the fabrication technique employed and the silicon substrate on the light detection capabilities of graphene-silicon Schottky diode photodetectors. The properties of devices are investigated over a broad wavelength range from near-UV to short-/mid-infrared radiation, radiation intensities covering over five orders of magnitude as well as the suitability of devices for high speed operation. Results show that the interfacial layer, depending on the required application, is in fact beneficial to enhance the photodetection properties of such devices. Further, we demonstrate the influence of the silicon substrate on the spectral response and operating speed. Fabricated devices operate over a broad spectral wavelength range from the near-UV to the short-/mid-infrared (thermal) wavelength regime, exhibit high photovoltage responses approaching 106 V W-1 and short rise- and fall-times of tens of nanoseconds.

The characteristics of reports to the police of child sexual abuse and the likelihood of cases proceeding to prosecution after delays in reporting.

Delays in disclosing and reporting child sexual abuse to the police are common, particularly among males and those who have been abused by clergy and others in a position of trust. This study, commissioned by the Royal Commission into Institutional Responses to Child Sexual Abuse, examined the patterns of timely and delayed reporting of sexual offences against children, and the likelihood of legal action commencing. De-identified unit record data for all sexual offences against children reported to the police over 20 years were obtained from official crime statistics agencies in two Australian states. While there were similarities between the two states in terms of the influence of public inquiries on reporting numbers over this period, and in the factors associated with delayed reporting, there were substantial differences in the likelihood of legal action being taken in cases reported by a child or adult complainants. In one state, legal action was more likely with increasing delay, until the delays extended to 10-20 years, after which the likelihood of legal action decreased. In the other state, the pattern was quite different - reports of sexual assault were somewhat more likely to result in legal action with immediate reporting. The least likely to proceed were cases involving young children in more recent years; long delays into adulthood were not necessarily adverse for prosecution.

Large-Scale Statistics for Threshold Optimization of Optically Pumped Nanowire Lasers.

Single nanowire lasers based on bottom-up III-V materials have been shown to exhibit room-temperature near-infrared lasing, making them highly promising for use as nanoscale, silicon-integrable, and coherent light sources. While lasing behavior is reproducible, small variations in growth conditions across a substrate arising from the use of bottom-up growth techniques can introduce interwire disorder, either through geometric or material inhomogeneity. Nanolasers critically depend on both high material quality and tight dimensional tolerances, and as such, lasing threshold is both sensitive to and a sensitive probe of such inhomogeneity. We present an all-optical characterization technique coupled to statistical analysis to correlate geometrical and material parameters with lasing threshold. For these multiple-quantum-well nanolasers, it is found that low threshold is closely linked to longer lasing wavelength caused by losses in the core, providing a route to optimized future low-threshold devices. A best-in-group room temperature lasing threshold of ∼43 µJ cm-2 under pulsed excitation was found, and overall device yields in excess of 50% are measured, demonstrating a promising future for the nanolaser architecture.