Sub-surface Imaging of Porous GaN Distributed Bragg Reflectors via Backscattered Electrons.

In this article, porous GaN distributed Bragg reflectors (DBRs) were fabricated by epitaxy of undoped/doped multilayers followed by electrochemical etching. We present backscattered electron scanning electron microscopy (BSE-SEM) for sub-surface plan-view imaging, enabling efficient, non-destructive pore morphology characterization. In mesoporous GaN DBRs, BSE-SEM images the same branching pores and Voronoi-like domains as scanning transmission electron microscopy. In microporous GaN DBRs, micrographs were dominated by first porous layer features (45 nm to 108 nm sub-surface) with diffuse second layer (153 nm to 216 nm sub-surface) contributions. The optimum primary electron landing energy (LE) for image contrast and spatial resolution in a Zeiss GeminiSEM 300 was approximately 20 keV. BSE-SEM detects porosity ca. 295 nm sub-surface in an overgrown porous GaN DBR, yielding low contrast that is still first porous layer dominated. Imaging through a ca. 190 nm GaN cap improves contrast. We derived image contrast, spatial resolution, and information depth expectations from semi-empirical expressions. These theoretical studies echo our experiments as image contrast and spatial resolution can improve with higher LE, plateauing towards 30 keV. BSE-SEM is predicted to be dominated by the uppermost porous layer's uppermost region, congruent with experimental analysis. Most pertinently, information depth increases with LE, as observed.

Core-Shell Nanorods as Ultraviolet Light-Emitting Diodes.

Existing barriers to efficient deep ultraviolet (UV) light-emitting diodes (LEDs) may be reduced or overcome by moving away from conventional planar growth and toward three-dimensional nanostructuring. Nanorods have the potential for enhanced doping, reduced dislocation densities, improved light extraction efficiency, and quantum wells free from the quantum-confined Stark effect. Here, we demonstrate a hybrid top-down/bottom-up approach to creating highly uniform AlGaN core-shell nanorods on sapphire repeatable on wafer scales. Our GaN-free design avoids self-absorption of the quantum well emission while preserving electrical functionality. The effective junctions formed by doping of both the n-type cores and p-type caps were studied using nanoprobing experiments, where we find low turn-on voltages, strongly rectifying behaviors and significant electron-beam-induced currents. Time-resolved cathodoluminescence measurements find short carrier liftetimes consistent with reduced polarization fields. Our results show nanostructuring to be a promising route to deep-UV-emitting LEDs, achievable using commercially compatible methods.

Three-Photon Excitation of InGaN Quantum Dots.

We demonstrate that semiconductor quantum dots can be excited efficiently in a resonant three-photon process, while resonant two-photon excitation is highly suppressed. Time-dependent Floquet theory is used to quantify the strength of the multiphoton processes and model the experimental results. The efficiency of these transitions can be drawn directly from parity considerations in the electron and hole wave functions in semiconductor quantum dots. Finally, we exploit this technique to probe intrinsic properties of InGaN quantum dots. In contrast to nonresonant excitation, slow relaxation of charge carriers is avoided, which allows us to measure directly the radiative lifetime of the lowest energy exciton states. Since the emission energy is detuned far from the resonant driving laser field, polarization filtering is not required and emission with a greater degree of linear polarization is observed compared to nonresonant excitation.

Mapping emission heterogeneity in layered halide perovskites using cathodoluminescence.

Recent advancements in the fabrication of layered halide perovskites and their subsequent modification for optoelectronic applications have ushered in a need for innovative characterisation techniques. In particular, heterostructures containing multiple phases and consequently featuring spatially defined optoelectronic properties are very challenging to study. Here, we adopt an approach centered on cathodoluminescence, complemented by scanning electron microscopy coupled with energy-dispersive x-ray spectroscopy analysis. Cathodoluminescence enables assessment of local emission variations by injecting charges with a nanometer-scale electron probe, which we use to investigate emission changes in three different systems: PEA2PbBr4, PEA2PbI4and lateral heterostructures of the two, fabricated via halide substitution. We identify and map different emission bands that can be correlated with local chemical composition and geometry. One emission band is characteristic of bromine-based halide perovskite, while the other originates from iodine-based perovskite. The coexistence of these emissions bands in the halide-substituted sample confirms the formation of lateral heterostructures. To improve the signal quality of the acquired data, we employed multivariate analysis, specifically the non-negative matrix factorization algorithm, on both cathodoluminescence and compositional datasets. The resulting understanding of the halide replacement process and identification of potential synergies in the optical properties will lead to optimised architectures for optoelectronic applications.

InGaN as a Substrate for AC Photoelectrochemical Imaging.

AC photoelectrochemical imaging at electrolyte-semiconductor interfaces provides spatially resolved information such as surface potentials, ion concentrations and electrical impedance. In this work, thin films of InGaN/GaN were used successfully for AC photoelectrochemical imaging, and experimentally shown to generate a considerable photocurrent under illumination with a 405 nm modulated diode laser at comparatively high frequencies and low applied DC potentials, making this a promising substrate for bioimaging applications. Linear sweep voltammetry showed negligible dark currents. The imaging capabilities of the sensor substrate were demonstrated with a model system and showed a lateral resolution of 7 microns.

Ultra-low-threshold InGaN/GaN quantum dot micro-ring lasers.

In this work, we demonstrate ultra-low-threshold, optically pumped, room-temperature lasing in GaN microdisk and micro-ring cavities containing InGaN quantum dots and fragmented quantum wells, with the lowest measured threshold at a record low of 6.2 µJ/cm2. When pump volume decreases, we observe a systematic decrease in the lasing threshold of micro-rings. The photon loss rate, γ, increases with increasing inner ring diameter, leading to a systematic decrease in the post-threshold slope efficiency, while the quality factor of the lasing mode remains largely unchanged. A careful analysis using finite-difference time-domain simulations attributes the increased γ to the loss of photons from lower-quality higher-order modes during amplified spontaneous emission.

Dislocations in AlGaN: Core Structure, Atom Segregation, and Optical Properties.

We conducted a comprehensive investigation of dislocations in Al0.46Ga0.54N. Using aberration-corrected scanning transmission electron microscopy and energy dispersive X-ray spectroscopy, the atomic structure and atom distribution at the dislocation core have been examined. We report that the core configuration of dislocations in AlGaN is consistent with that of other materials in the III-Nitride system. However, we observed that the dissociation of mixed-type dislocations is impeded by alloying GaN with AlN, which is confirmed by our experimental observation of Ga and Al atom segregation in the tensile and compressive parts of the dislocations, respectively. Investigation of the optical properties of the dislocations shows that the atom segregation at dislocations has no significant effect on the intensity recorded by cathodoluminescence in the vicinity of the dislocations. These results are in contrast with the case of dislocations in In0.09Ga0.91N where segregation of In and Ga atoms also occurs but results in carrier localization limiting non-radiative recombination at the dislocation. This study therefore sheds light on why InGaN-based devices are generally more resilient to dislocations than their AlGaN-based counterparts.

Ultrafast, Polarized, Single-Photon Emission from m-Plane InGaN Quantum Dots on GaN Nanowires.

We demonstrate single-photon emission from self-assembled m-plane InGaN quantum dots (QDs) embedded on the side-walls of GaN nanowires. A combination of electron microscopy, cathodoluminescence, time-resolved microphotoluminescence (µPL), and photon autocorrelation experiments give a thorough evaluation of the QD structural and optical properties. The QD exhibits antibunched emission up to 100 K, with a measured autocorrelation function of g(2)(0) = 0.28(0.03) at 5 K. Studies on a statistically significant number of QDs show that these m-plane QDs exhibit very fast radiative lifetimes (260 ± 55 ps) suggesting smaller internal fields than any of the previously reported c-plane and a-plane QDs. Moreover, the observed single photons are almost completely linearly polarized aligned perpendicular to the crystallographic c-axis with a degree of linear polarization of 0.84 ± 0.12. Such InGaN QDs incorporated in a nanowire system meet many of the requirements for implementation into quantum information systems and could potentially open the door to wholly new device concepts.

Nanocomposites of TiO2/cyanoethylated cellulose with ultra high dielectric constants.

A novel dielectric nanocomposite containing a high permittivity polymer, cyanoethylated cellulose (CRS) and TiO2 nanoparticles was successfully prepared with different weight percentages (10%, 20% and 30%) of TiO2. The intermolecular interactions and morphology within the polymer nanocomposites were analysed. TiO2/CRS nanofilms on SiO2/Si wafers were used to form metal-insulator-metal type capacitors. Capacitances and loss factors in the frequency range of 1 kHz-1 MHz were measured. At 1 kHz CRS-TiO2 nanocomposites exhibited ultra high dielectric constants of 118, 176 and 207 for nanocomposites with 10%, 20% and 30% weight of TiO2 respectively, significantly higher than reported values of pure CRS (21), TiO2 (41) and other dielectric polymer-TiO2 nanocomposite films. Furthermore, all three CRS-TiO2 nanocomposites show a loss factor <0.3 at 1 kHz and low leakage current densities (10(-6)-10(-7) A cm(-2)). Leakage was studied using conductive atomic force microscopy and it was observed that the leakage is associated with TiO2 nanoparticles embedded in the CRS polymer matrix. A new class of ultra high dielectric constant hybrids using nanoscale inorganic dielectrics dispersed in a high permittivity polymer suitable for energy management applications is reported.

A study of the optical and polarisation properties of InGaN/GaN multiple quantum wells grown on a-plane and m-plane GaN substrates.

We report on a comparative study of the low temperature emission and polarisation properties of InGaN/GaN quantum wells grown on nonpolar ([Formula: see text]) a-plane and ([Formula: see text]) m-plane free-standing bulk GaN substrates where the In content varied from 0.14 to 0.28 in the m-plane series and 0.08 to 0.21 for the a-plane series. The low temperature photoluminescence spectra from both sets of samples are broad with full width at half maximum height increasing from 81 to 330 meV as the In fraction increases. Photoluminescence excitation spectroscopy indicates that the recombination mainly involves strongly localised carriers. At 10 K the degree of linear polarisation of the a-plane samples is much smaller than of the m-plane counterparts and also varies across the spectrum. From polarisation-resolved photoluminescence excitation spectroscopy we measured the energy splitting between the lowest valence sub-bands to lie in the range of 23-54 meV for the a- and m-plane samples in which we could observe distinct exciton features. Thus the thermal occupation of a higher valence sub-band cannot be responsible for the reduction of the degree of linear polarisation at 10 K. Time-resolved spectroscopy indicates that in a-plane samples there is an extra emission component which is at least partly responsible for the reduction in the degree of linear polarisation.

Nanocathodoluminescence Reveals Mitigation of the Stark Shift in InGaN Quantum Wells by Si Doping.

Nanocathodoluminescence reveals the spectral properties of individual InGaN quantum wells in high efficiency light emitting diodes. We observe a variation in the emission wavelength of each quantum well, in correlation with the Si dopant concentration in the quantum barriers. This is reproduced by band profile simulations, which reveal the reduction of the Stark shift in the quantum wells by Si doping. We demonstrate nanocathodoluminescence is a powerful technique to optimize doping in optoelectronic devices.

Practical Issues for Atom Probe Tomography Analysis of III-Nitride Semiconductor Materials.

Various practical issues affecting atom probe tomography (APT) analysis of III-nitride semiconductors have been studied as part of an investigation using a c-plane InAlN/GaN heterostructure. Specimen preparation was undertaken using a focused ion beam microscope with a mono-isotopic Ga source. This enabled the unambiguous observation of implantation damage induced by sample preparation. In the reconstructed InAlN layer Ga implantation was demonstrated for the standard "clean-up" voltage (5 kV), but this was significantly reduced by using a lower voltage (e.g., 1 kV). The characteristics of APT data from the desorption maps to the mass spectra and measured chemical compositions were examined within the GaN buffer layer underlying the InAlN layer in both pulsed laser and pulsed voltage modes. The measured Ga content increased monotonically with increasing laser pulse energy and voltage pulse fraction within the examined ranges. The best results were obtained at very low laser energy, with the Ga content close to the expected stoichiometric value for GaN and the associated desorption map showing a clear crystallographic pole structure.

Coincident electron channeling and cathodoluminescence studies of threading dislocations in GaN.

We combine two scanning electron microscopy techniques to investigate the influence of dislocations on the light emission from nitride semiconductors. Combining electron channeling contrast imaging and cathodoluminescence imaging enables both the structural and luminescence properties of a sample to be investigated without structural damage to the sample. The electron channeling contrast image is very sensitive to distortions of the crystal lattice, resulting in individual threading dislocations appearing as spots with black-white contrast. Dislocations giving rise to nonradiative recombination are observed as black spots in the cathodoluminescence image. Comparison of the images from exactly the same micron-scale region of a sample demonstrates a one-to-one correlation between the presence of single threading dislocations and resolved dark spots in the cathodoluminescence image. In addition, we have also obtained an atomic force microscopy image from the same region of the sample, which confirms that both pure edge dislocations and those with a screw component (i.e., screw and mixed dislocations) act as nonradiative recombination centers for the Si-doped c-plane GaN thin film investigated.

Scanning capacitance microscopy of GaN-based high electron mobility transistor structures: A practical guide.

The scanning capacitance microscope (SCM) is a powerful tool to characterise local electrical properties in GaN-based high electron mobility transistor (HEMT) structures with nanoscale resolution. We investigated the experimental setup and the imaging conditions to optimise the SCM contrast. As to the experimental setup, we show that the desired tip should be sharp (e.g., with the tip radius of ≤25nm) and its coating should be made of conductive doped diamond. Most importantly, its spring constant should be large to achieve stable tip-sample contact. The selected tip should be positioned close to both the edge and Ohmic contact of the sample. Regarding the imaging conditions, we also show that a dc bias should be applied in addition to an ac bias because the latter alone is not sufficient to deplete the two-dimensional electron gas (2DEG) in the AlGaN/GaN heterostructure. The approximate range of the effective dc bias values was found by measuring the local dC/dV-V curves, yielding, after further optimisation, two optimised dc bias values which provide strong, but opposite, SCM contrast. In comparison, the selected ac bias value has no significant impact on the SCM contrast. The described methodology could potentially also be applied to other types of HEMT structures, and highly-doped samples.

Monitoring of the Initial Stages of Diamond Growth on Aluminum Nitride Using In Situ Spectroscopic Ellipsometry.

The high thermal conductivity of polycrystalline diamond makes it ideally suited for thermal management solutions for gallium nitride (GaN) devices, with a diamond layer grown on an aluminum nitride (AlN) interlayer atop the GaN stack. However, this application is limited by the thermal barrier at the interface between diamond and substrate, which has been associated with the transition region formed in the initial phases of growth. In this work, in situ spectroscopic ellipsometry (SE) is employed to monitor early-stage microwave plasma-enhanced chemical vapor deposition diamond growth on AlN. An optical model was developed from ex situ spectra and applied to spectra taken in situ during growth. Coalescence of separate islands into a single film was marked by a reduction in bulk void fraction prior to a spike in sp2 fraction due to grain boundary formation. Parameters determined by the SE model were corroborated using Raman spectroscopy and atomic force microscopy.

Dielectric behaviour of plasma hydrogenated TiO2/cyanoethylated cellulose nanocomposites.

The interface between the polymer and nanoparticle has a vital role in determining the overall dielectric properties of a dielectric polymer nanocomposite. In this study, a novel dielectric nanocomposite containing a high permittivity polymer, cyanoethylated cellulose (CRS) and TiO2 nanoparticles surface modified by hydrogen plasma treatments was successfully prepared with different weight percentages (10%, 20% and 30%) of hydrogenated TiO2. Internal structure of H plasma treated TiO2 nanoparticles (H-TiO2) and the intermolecular interactions and morphology within the polymer nanocomposites were analysed. H-TiO2/CRS thin films on SiO2/Si wafers were used to form metal-insulator-metal (MIM) type capacitors. Capacitances and loss factors in the frequency range of 1 kHz to 1 MHz were measured. At 1 kHz H-TiO2/CRS nanocomposites exhibited ultra-high dielectric constants of 80, 118 and 131 for nanocomposites with 10%, 20% and 30% weight of hydrogenated TiO2 respectively, significantly higher than values of pure CRS (21) and TiO2 (41). Furthermore, all three H-TiO2 /CRS nanocomposites show a loss factor <0.3 at 1 kHz and low leakage current densities (10-6 A cm-2-10-7 A cm-2). Leakage was studied using conductive atomic force microscopy (C-AFM) and it was observed that the leakage is associated with H-TiO2 nanoparticles embedded in the CRS polymer matrix. Although, modified interface slightly reduces energy densities compared to pristine TiO2/CRS system, the capacitance values for H-TiO2/CRS-in the voltage range of -2 V to 2 V are very stable. Whilst H-TiO2/CRS possesses ultra-high dielectric constants (>100), this study reveals that the polymer nanoparticle interface has a potential influence on dielectric behaviour of the composite.

Complications in silane-assisted GaN nanowire growth.

Understanding the growth mechanisms of III-nitride nanowires is of great importance to realise their full potential. We present a systematic study of silane-assisted GaN nanowire growth on c-sapphire substrates by investigating the surface evolution of the sapphire substrates during the high temperature annealing, nitridation and nucleation steps, and the growth of GaN nanowires. The nucleation step - which transforms the AlN layer formed during the nitridation step to AlGaN - is critical for subsequent silane-assisted GaN nanowire growth. Both Ga-polar and N-polar GaN nanowires were grown with N-polar nanowires growing much faster than the Ga-polar nanowires. On the top surface of the N-polar GaN nanowires protuberance structures were found, which relates to the presence of Ga-polar domains within the nanowires. Detailed morphology studies revealed ring-like features concentric with the protuberance structures, indicating energetically favourable nucleation sites at inversion domain boundaries. Cathodoluminescence studies showed quenching of emission intensity at the protuberance structures, but the impact is limited to the protuberance structure area only and does not extend to the surrounding areas. Hence it should minimally affect the performance of devices whose functions are based on radial heterostructures, suggesting that radial heterostructures remain a promising device structure.

Additive GaN Solid Immersion Lenses for Enhanced Photon Extraction Efficiency from Diamond Color Centers.

Effective light extraction from optically active solid-state spin centers inside high-index semiconductor host crystals is an important factor in integrating these pseudo-atomic centers in wider quantum systems. Here, we report increased fluorescent light collection efficiency from laser-written nitrogen-vacancy (NV) centers in bulk diamond facilitated by micro-transfer printed GaN solid immersion lenses. Both laser-writing of NV centers and transfer printing of micro-lens structures are compatible with high spatial resolution, enabling deterministic fabrication routes toward future scalable systems development. The micro-lenses are integrated in a noninvasive manner, as they are added on top of the unstructured diamond surface and bonded by van der Waals forces. For emitters at 5 µm depth, we find approximately 2× improvement of fluorescent light collection using an air objective with a numerical aperture of NA = 0.95 in good agreement with simulations. Similarly, the solid immersion lenses strongly enhance light collection when using an objective with NA = 0.5, significantly improving the signal-to-noise ratio of the NV center emission while maintaining the NV's quantum properties after integration.

Unintentional doping in GaN.

The optimisation of GaN-based electronic and optoelectronic devices requires control over the doping of the material. However, device performance, particular for lateral transport electronic devices, is degraded by the presence of unintentional doping, which for heteroepitaxial GaN layers grown in the polar (0001) orientation is mainly confined to a layer adjacent to the GaN/substrate interface. The use of scanning capacitance microscopy (SCM) has demonstrated that this layer forms due to the high rate of incorporation of gas phase impurities, primarily oxygen, during the early stages of growth, when N-rich semi-polar facets are often present. The presence of such facets leads to additional unintentional doping when defect density reduction strategies involving a three-dimensional growth phase (such as epitaxial lateral overgrowth) are employed. Many semi-polar epitaxial layers, on the other hand, exhibit significant unintentional doping throughout their thickness, except when a three-dimensional growth phase is introduced to aid in defect density reduction resulting in the presence of (0001) and non-polar facets which incorporate less dopant. Non-polar epitaxial samples exhibit behaviour more similar to (0001)-oriented material, but oxygen diffusion from the sapphire substrate along prismatic stacking faults also locally affects the extent of the unintentional doping in this case.