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We investigate the strain state of ensembles of thin and nearly coalescence-free self-assembled GaN nanowires prepared by plasma-assisted molecular beam epitaxy on Ti/Al2O3(0001) substrates. The shifts of Bragg peaks in high-resolution X-ray diffraction profiles reveal the presence of a homogeneous tensile strain in the out-of-plane direction. This strain is inversely proportional to the average nanowire radius and results from the surface stress acting on the nanowire sidewalls. The superposition of strain from nanowires with different radii in the same ensemble results in a broadening of the Bragg peaks that mimics an inhomogeneous strain on a macroscopic scale. The nanowire ensembles show a small blueshift of the bound-exciton transitions in photoluminescence spectra, reflecting the existence of a compensating in-plane compressive strain, as further supported by grazing incidence X-ray diffraction measurements carried out at a synchrotron. By combining X-ray diffraction and photoluminescence spectroscopy, the surface stress components fx and fz of the air-exposed GaN { 1 1 ¯ 00 } planes that constitute the nanowire sidewalls are determined experimentally to be 2.25 and − 0.7 N/m, respectively.

We study the cross-sectional shape of GaN nanowires (NWs) by transmission electron microscopy. The shape is examined at different heights of long NWs, as well as at the same height for NWs of different lengths. Two distinct trends in the evolution of the cross-sectional shape along the NW length are observed. At the top, merging NWs develop common {11̄00} side facets. At the bottom, the NWs acquire roundish shapes. This observation is explained by the entirely different NW environments at the top and the bottom of the NWs. At the top, NWs are exposed to the Ga and N atomic fluxes giving rise to axial growth, resulting in the equilibrium growth shape with zero growth rate at the {11̄00} facets. At the bottom, NWs are shadowed from the impinging fluxes and are only annealed, allowing them to eventually approach the equilibrium crystal shape. The study of identical samples by grazing incidence small-angle X-ray scattering independently confirms these trends in the shape evolution of the sidewall facets.

Several of the key issues of planar (Al,Ga)N-based deep-ultraviolet light emitting diodes could potentially be overcome by utilizing nanowire heterostructures, exhibiting high structural perfection and improved light extraction. Here, we study the spontaneous emission of GaN/(Al,Ga)N nanowire ensembles grown on Si(111) by plasma-assisted molecular beam epitaxy. The nanowires contain single GaN quantum disks embedded in long (Al,Ga)N nanowire segments essential for efficient light extraction. These quantum disks are found to exhibit intense emission at unexpectedly high energies, namely, significantly above the GaN bandgap, and almost independent of the disk thickness. An in-depth investigation of the actual structure and composition of the nanowires reveals a spontaneously formed Al gradient both along and across the nanowire, resulting in a complex core/shell structure with an Al deficient core and an Al rich shell with continuously varying Al content along the entire length of the (Al,Ga)N segment. This compositional change along the nanowire growth axis induces a polarization doping of the shell that results in a degenerate electron gas in the disk, thus screening the built-in electric fields. The high carrier density not only results in the unexpectedly high transition energies, but also in radiative lifetimes depending only weakly on temperature, leading to a comparatively high internal quantum efficiency of the GaN quantum disks up to room temperature., This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Nano Letters (2019), copyright (C) American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acs.nanolett.9b01521, the supporting information is available (free of charge) under the same link

We report on the optoelectronic properties of GaN$(0001)$ and $(1\bar{1}00)$ surfaces after their functionalization with phosphonic acid derivatives. To analyze the possible correlation between the acid's electronegativity and the GaN surface band bending, two types of phosphonic acids, n-octylphosphonic acid (OPA) and 1H,1H,2H,2H-perfluorooctanephosphonic acid (PFOPA), are grafted on oxidized GaN$(0001)$ and GaN$(1\bar{1}00)$ layers as well as on GaN nanowires. The resulting hybrid inorganic/organic heterostructures are investigated by X-ray photoemission and photoluminescence spectroscopy. The GaN work function is changed significantly by the grafting of phosphonic acids, evidencing the formation of dense self-assembled monolayers. Regardless of the GaN surface orientation, both types of phosphonic acids significantly impact the GaN surface band bending. A dependence on the acids' electronegativity is, however, only observed for the oxidized GaN$(1\bar{1}00)$ surface, indicating a relatively low density of surface states and a favorable band alignment between the surface oxide and acids' electronic states. Regarding the optical properties, the covalent bonding of PFOPA and OPA on oxidized GaN layers and nanowires significantly affect their external quantum efficiency, especially in the nanowire case due to the large surface-to-volume ratio. The variation in the external quantum efficiency is related to the modication of both the internal electric fields and surface states. These results demonstrate the potential of phosphonate chemistry for the surface functionalization of GaN, which could be exploited for selective sensing applications.

GaN nanowires grown by molecular beam epitaxy generally suffer from dominant nonradiative recombination, which is believed to originate from point defects. To suppress the formation of these defects, we explore the synthesis of GaN nanowires at temperatures up to 915 °C enabled by the use of thermally stable TiNx/Al2O3 substrates. These samples exhibit indeed bound exciton decay times approaching those measured for state-of-the-art bulk GaN. However, the decay time is not correlated with the growth temperature, but rather with the nanowire diameter. The inverse dependence of the decay time on diameter suggests that the nonradiative process in GaN nanowires is not controlled by the defect density, but by the field ionization of excitons in the radial electric field caused by surface band bending. We propose a unified mechanism accounting for nonradiative recombination in GaN nanowires of arbitrary diameter.

The intensity of small-angle X-ray scattering from GaN nanowires on Si(111) depends on the orientation of the side facets with respect to the incident beam. This reminiscence of truncation rod scattering gives rise to a deviation from Porod’s law. A roughness of just 3–4 atomic steps per micrometre-long side facet notably changes the intensity curves., Small-angle X-ray scattering from GaN nanowires grown on Si(111) is measured in the grazing-incidence geometry and modelled by means of a Monte Carlo simulation that takes into account the orientational distribution of the faceted nanowires and the roughness of their side facets. It is found that the scattering intensity at large wavevectors does not follow Porod’s law I(q) ∝ q −4. The intensity depends on the orientation of the side facets with respect to the incident X-ray beam. It is maximum when the scattering vector is directed along a facet normal, reminiscent of surface truncation rod scattering. At large wavevectors q, the scattering intensity is reduced by surface roughness. A root-mean-square roughness of 0.9 nm, which is the height of just 3–4 atomic steps per micrometre-long facet, already gives rise to a strong intensity reduction.

We analyse the morphological, structural and luminescence properties of self-assembled ZnO nanowires grown by chemical vapour transport on Si(001). The examination of nanowire ensembles by scanning electron microscopy reveals that a non-negligible fraction of nanowires merge together forming coalesced aggregates during growth. We show that the coalescence degree can be unambiguously quantified by a statistical analysis of the cross-sectional shape of the nanowires. The examination of the structural properties by X-ray diffraction evidences that the nanowires crystallize in the wurtzite phase, elongate along the c-axis, and are randomly oriented in plane. The luminescence of the ZnO nanowires, investigated by photoluminescence and cathodoluminescence spectroscopies, is characterized by two bands, the nearband-edge emission and the characteristic defect-related green luminescence of ZnO. The cross-correlation of scanning electron micrographs and monochromatic cathodoluminescence intensity maps reveals that: (i) coalescence joints act as a source of non-radiative recombination, and (ii) the luminescence of ZnO nanowires is inhomogeneously distributed at the single nanowire level. Specifically, the near-band-edge emission arises from the nanowire cores, while the defect-related green luminescence originates from the volume close to the nanowire sidewalls. Two-dimensional simulations of the optical guided modes supported by ZnO nanowires allow us to exclude waveguiding effects as the underlying reason for the luminescence inhomogeneities. We thus attribute this observation to the formation of a core-shell structure in which the shell is characterized by a high concentration of green-emitting radiative point defects with respect to the core.

We demonstrate the top-down fabrication of ordered arrays of GaN nanowires by selective area sublimation of pre-patterned GaN(0001) layers grown by hydride vapor phase epitaxy on Al$_{2}$O$_{3}$. Arrays with nanowire diameters and spacings ranging from 50 to 90 nm and 0.1 to 0.7 $\mu$m, respectively, are simultaneously produced under identical conditions. The sublimation process, carried out under high vacuum conditions, is analyzed \emph{in situ} by reflection high-energy electron diffraction and line-of-sight quadrupole mass spectromety. During the sublimation process, the GaN(0001) surface vanishes, giving way to the formation of semi-polar $\lbrace1\bar{1}03\rbrace$ facets which decompose congruently following an Arrhenius temperature dependence with an activation energy of ($3.54 \pm 0.07$) eV and an exponential prefactor of $1.58\times10^{31}$ atoms cm$^{-2}$ s$^{-1}$. The analysis of the samples by low-temperature cathodoluminescence spectroscopy reveals that, in contrast to dry etching, the sublimation process does not introduce nonradiative recombination centers at the nanowire sidewalls. This technique is suitable for the top-down fabrication of a variety of ordered nanostructures, and could possibly be extended to other material systems with similar crystallographic properties such as ZnO., Comment: This is the accepted manuscript version of an article that appeared in Nanoscale Advances. The CC BY-NC 3.0 license applies, see http://creativecommons.org/licenses/by-nc/3.0/

We analyze the temporal variation of the substrate optical reflectance during the formation of GaN nanowires in molecular beam epitaxy using transverse electric and transverse magnetic polarized light. The time dependence of the reflectance signal is simulated using an effective medium approach that takes into account the spatial fluctuations in the length and density of the nanowire ensemble within the area probed by the laser beam. Our study demonstrates that optical reflectometry is a powerful technique to detect the onset of nanowire nucleation, assess the deposition rate, and estimate the fluctuations in the nanowire length and covered area fraction at the μm scale.

We demonstrate an all-epitaxial and scalable growth approach to fabricate single-crystalline GaN nanowires on graphene by plasma-assisted molecular beam epitaxy. As substrate, we explore several types of epitaxial graphene layer structures synthesized on SiC. The different structures differ mainly in their total number of graphene layers. Because graphene is found to be etched under active N exposure, the direct growth of GaN nanowires on graphene is only achieved on multilayer graphene structures. The analysis of the nanowire ensembles prepared on multilayer graphene by Raman spectroscopy and transmission electron microscopy reveals the presence of graphene underneath as well as in between nanowires, as desired for the use of this material as contact layer in nanowire-based devices. The nanowires nucleate preferentially at step edges, are vertical, well aligned, epitaxial, and of comparable structural quality as similar structures fabricated on conventional substrates.

In a combined experimental and theoretical study, we investigate the influence of the material source arrangement in a molecular beam epitaxy system on the growth of nanowire (NW) core-shell structures. In particular, we study the shell growth of GaN around GaN template NWs under the boundary condition that Ga and N do not impinge on a given sidewall facet at the same time. Our experiments with different V/III ratios and substrate temperatures show that obtaining shells with homogeneous thickness along the whole NW length is not straightforward. Analyzing in detail the shell morphology with and without substrate rotation, we find that the different azimuthal angles of the sources have a major impact on the Ga adatom kinetics and the final shell morphology. In general, growth is possible only under directly impinging N, and Ga adatoms diffuse between the sidewalls and the top facet as well as the substrate, but not between adjacent sidewall facets. On the basis of these experimental results, we develop a diffusion model which takes into account different NW facets and the substrate. The model allows to describe well the experimental shell profiles and predicts that homogeneous shell growth can be achieved if the Ga and N sources are arranged next to each other or for very high rotation speeds. Moreover, the modeling reveals that the growth on a given side facet can be categorized within one rotation in four different phases: the Ga wetting phase, the metal-rich growth phase, the N-rich growth phase, and the dissociation phase. The striking difference to growth processes on planar samples is that, in our case, diffusion takes place between different regions, i.e. the sidewall vs the top facet and substrate, out of which on one N impinges not continuously, resulting in complex gradients in chemical potential that are modulated in time by substrate rotation. The comprehensiveness of our model provides a deep understanding of diffusion processes and the resulting adatom concentration, and could be applied to other three-dimensional structures and material systems.

We present a conceptually novel approach to achieve selective area epitaxy of GaN nanowires. The approach is based on the fact that these nanostructures do not form in plasma-assisted molecular beam epitaxy on structurally and chemically uniform cation-polar substrates. By in situ depositing and nitridating Si on a Ga-polar GaN film, we locally reverse the polarity to induce the selective area epitaxy of N-polar GaN nanowires. We show that the nanowire number density can be controlled over several orders of magnitude by varying the amount of predeposited Si. Using this growth approach, we demonstrate the synthesis of single-crystalline and uncoalesced nanowires with diameters as small as 20 nm. The achievement of nanowire number densities low enough to prevent the shadowing of the nanowire sidewalls from the impinging fluxes paves the way for the realization of homogeneous core-shell heterostructures without the need of using ex situ prepatterned substrates.

We investigate the nucleation, growth, and coalescence of spontaneously formed GaN nanowires in molecular beam epitaxy combining the statistical analysis of scanning electron micrographs with Monte Carlo growth models. We find that (i) the nanowire density is limited by the shadowing of the substrate from the impinging fluxes by already existing nanowires, (ii) shortly after the nucleation stage, nanowire radial growth becomes negligible, and (iii) coalescence is caused by bundling of nanowires. The latter phenomenon is driven by the gain of surface energy at the expense of the elastic energy of bending and becomes energetically favorable once the nanowires exceed a certain critical length.

We study the growth of InN films on In 2 O 3 (111) substrates by plasma-assisted molecular beam epitaxy under N excess. InN films deposited directly on In 2 O 3 (111) exhibit a strongly faceted morphology. A nitridation step prior to growth is found to convert the In 2 O 3 (111) surface to InN{0001}. The morphology of InN films deposited on such nitridated In 2 O 3 (111) substrates is characteristic for growth by instable step-flow and is thus drastically different from the three-dimensional growth obtained without nitridation. We show that this change originates from the different polarity of the films: while InN films deposited directly on In 2 O 3 (111) are In-polar, they are N-polar when grown on the nitridated substrate.

Correction to Absence of Quantum-Confined Stark Effect in GaN Quantum Disks Embedded in (Al,Ga)N Nanowires Grown by Molecular Beam Epitaxy

In this work, we demonstrate the possibility of controlling the orientation of the top-facets of GaN nanowires grown by plasma-assisted molecular beam epitaxy by means of an in situ thermal treatment at temperatures in the 800--910 ${}^{\ensuremath{\circ}}\text{C}$ range, at which the material decomposes with a non-negligible rate. Depending on whether the process is carried out under vacuum or active nitrogen exposure, the nanowires can develop either ${1\overline{1}0\overline{2}}$ or ${1\overline{1}0\overline{8}}$ semipolar top-facets. The shape transformation is reversible; namely, the original $(000\overline{1})$ polar facets of as-grown nanowires can be recovered after further GaN growth. Using reflection high-energy electron diffraction, the reshaping process is monitored in vivo by tracking the formation and subsequent evolution of chevrons in the diffraction pattern. This analysis reveals that the reshaping takes place after a certain delay time that can last up to several tens of minutes. It also evidences that the shape transformation is not abrupt; instead there is a continuous evolution from high- to low-index semipolar facets. We observe energy barriers higher than 3 eV along the reshaping path toward the ${1\overline{1}0\overline{2}}$ top-facets. The formation of ${1\overline{1}0\overline{8}}$ top-facets is assigned to an intermediate energy minimum along the reshaping path where the system freezes in the presence of active nitrogen. A change in the Ga chemical potential at the nanowire tip is proposed as the trigger for the reshaping, a process that could be either thermodynamically or kinetically driven. The formation of semipolar facets after thermal decomposition is also observed for $\mathrm{GaN}(000\overline{1})$ layers, demonstrating that the reshaping process is not related to the peculiar nanowire morphology. This unprecedented ability to form semipolar facets at the tip of N-polar GaN nanowires may pave the way for the fabrication of semipolar axial nanowire heterostructures along the $[000\overline{1}]$ direction.

We investigate the formation of GaN nanowires in plasma-assisted molecular beam epitaxy on epitaxial graphene prepared on SiC(0001) using the surface graphitization method in an inductively heated furnace. The pristine graphene layer structure is characterized by the presence of atomically flat terraces and steps which are covered by single-layer and bi-layer graphene, respectively. The formation of GaN is investigated under N-rich growth conditions for substrate temperatures between 725 and 800°C. Regardless of the substrate temperature, graphene is found to degrade during GaN growth due to its exposure to the N plasma. The morphology of the samples varies significantly between the regions originally covered with single-layer and bi-layer graphene. Specifically, on the terraces GaN grows as a Ga-polar layer, while along the step edges it forms meandering rows of N-polar nanowires. The formation of N-polar GaN nanowires on the cation-polar SiC substrate is explained in terms of a C-induced polarity inversion. Due to the superior thermal stability of N-polar material, it is possible to exclusively form nanowires along the step edges when using elevated substrate temperatures. Therefore, the investigated graphene layer structure enables the self-assembled formation of well-separated rows of GaN nanowires.

The realization of semiconductor structures with stable excitons at room temperature is crucial for the development of excitonics and polaritonics. Quantum confinement has commonly been employed for enhancing excitonic effects in semiconductor heterostructures. Dielectric confinement, which gives rises to much stronger enhancement, has proven to be more difficult to achieve because of the rapid nonradiative surface/interface recombination in hybrid dielectric-semiconductor structures. Here, we demonstrate intense excitonic emission from bare GaN nanowires with diameters down to 6 nm. The large dielectric mismatch between the nanowires and vacuum greatly enhances the Coulomb interaction, with the thinnest nanowires showing the strongest dielectric confinement and the highest radiative efficiency at room temperature. In situ monitoring of the fabrication of these structures allows one to accurately control the degree of dielectric enhancement. These ultrathin nanowires may constitute the basis for the fabrication of advanced low-dimensional structures with an unprecedented degree of confinement.

We present an innovative approach to integrate arrays of isolated, strain-free GaN crystals on patterned Si substrates. First, micrometer-sized pillars are patterned onto Si(0 0 1) substrates. Subsequently, 2.5 μm Si substrates are deposited by low-energy plasma-enhanced chemical vapor deposition, forming crystals mostly bounded by {1 1 1}, {1 1 3}, and {15 3 23} facets. Plasma-assisted molecular beam epitaxy is then used for GaN deposition. GaN crystals with slanted {0 0 0 1} facets having a root-mean-square surface roughness of 0.7 nm are obtained for a deposited material thickness of >3 μm. Microphotoluminescence measurements performed at room and cryogenic temperature show no yellow luminescence and a neutral donor-bound A exciton transition at 3.471 eV (10 K) with a full width at half-maximum of 10 meV. Microphotoluminescence and micro-Raman spectra reveal that GaN grown on Si pillars is strain-free. Our results indicate that the shape of GaN crystals can be tuned by the pattern periodicity and that a reduction of threading dislocations is achieved in their top part.

In molecular beam epitaxy, the spontaneous formation of GaN nanowires on Si(111) substrates at elevated temperatures is limited by the long incubation time that precedes nanowire nucleation. In this work, we present three growth approaches to minimize the incubation time and to thus facilitate significantly higher growth temperatures (up to 875 °C). We achieve this advancement by (i) using III/V flux ratios of >1 to compensate for Ga desorption, (ii) introducing a two-step growth procedure, and (iii) using an AlN buffer layer to favor GaN nucleation. The GaN nanowire ensembles grown at so far unexplored substrate temperatures exhibit excitonic transitions with sub-meV linewidths comparable to those of state-of-the-art free-standing GaN layers grown by hydride vapor phase epitaxy.

Vertical GaN nanowires are grown in a self-induced way on a sputtered Ti film by plasma-assisted molecular beam epitaxy. Both in situ electron diffraction and ex situ ellipsometry show that Ti is converted to TiN upon exposure of the surface to the N plasma. In addition, the ellipsometric data demonstrate this TiN film to be metallic. The diffraction data evidence that the GaN nanowires have a strict epitaxial relationship to this film. Photoluminescence spectroscopy of the GaN nanowires shows excitonic transitions virtually identical in spectral position, line width, and decay time to those of state-of-the-art GaN nanowires grown on Si. Therefore, the crystalline quality of the GaN nanowires grown on metallic TiN and on Si is equivalent. The freedom to employ metallic substrates for the epitaxial growth of semiconductor nanowires in high structural quality may enable novel applications that benefit from the associated high thermal and electrical conductivity as well as optical reflectivity.

We investigate in detail the self-assembled nucleation and growth of GaN nanowires by molecular beam epitaxy on crystalline TiN films. We demonstrate that this type of substrate allows the growth of long and thin GaN nanowires that do not suffer from coalescence, which is in contrast to the growth on Si and other substrates. Only beyond a certain nanowire length that depends on the nanowire number density and exceeds here 1.5 {\mu}m, coalescence takes place by bundling, i.e. the same process as on Si. By analyzing the nearest neighbor distance distribution, we identify diffusion-induced repulsion of neighboring nanowires as the main mechanism limiting the nanowire number density during nucleation on TiN. Since on Si the final number density is determined by shadowing of the impinging molecular beams by existing nanowires, it is the difference in adatom surface diffusion that enables on TiN the formation of nanowire ensembles with reduced number density. These nanowire ensembles combine properties that make them a promising basis for the growth of core-shell heterostructures., Comment: The final publication is available at link.springer.com

In semiconductor quantum-wire heterostructures, interface roughness leads to exciton localization and to a radiative decay rate much smaller than that expected for structures with flat interfaces. Here, we uncover the electronic and optical properties of the one-dimensional extended defects that form at the intersection between stacking faults and inversion domain boundaries in GaN nanowires. We show that they act as crystal-phase quantum wires, a novel one-dimensional quantum system with atomically flat interfaces. These quantum wires efficiently capture excitons whose radiative decay gives rise to an optical doublet at 3.36 eV at 4.2 K. The binding energy of excitons confined in crystal-phase quantum wires is measured to be more than twice larger than that of the bulk. As a result of their unprecedented interface quality, these crystal-phase quantum wires constitute a model system for the study of one-dimensional excitons.

Single GaN nanowires formed spontaneously on a given substrate represent nanoscopic single crystals free of any extended defects. However, due to the high area density of thus formed GaN nanowire ensembles, individual nanowires coalesce with others in their immediate vicinity. This coalescence process may introduce strain and structural defects, foiling the idea of defect-free material due to the nanowire geometry. To investigate the consequences of this process, a quantitative measure of the coalescence of nanowire ensembles is required. We derive objective criteria to determine the coalescence degree of GaN nanowire ensembles. These criteria are based on the area-perimeter relationship of the cross-sectional shapes observed, and in particular on their circularity. Employing these criteria, we distinguish single nanowires from coalesced aggregates in an ensemble, determine the diameter distribution of both, and finally analyze the coalescence degree of nanowire ensembles with increasing fill factor.

We report on the electronic properties of GaN ( 1 1 ¯ 00 ) and (0001) surfaces after three different and subsequent device processing compatible cleaning steps: HCl etching, annealing at 400 °C in N2 atmosphere, and O2 plasma exposure. The surface electronic properties are quantified, in the dark and under ultraviolet illumination, using X-ray photoelectron spectroscopy and a Kelvin probe. We find that the cleaning steps largely affect the work function and the band bending of both GaN orientations. These modifications are attributed to the presence of different surface states as well as to the formation of adsorbates building up distinct surface dipoles. Besides these results, we detect that under ultraviolet illumination the work function of the surfaces exposed to HCl decreases by at least 0.2 eV without screening of the band bending. We thus attribute the observed surface photovoltage to a photo-induced modification of the surface dipole. Overall, these results emphasize the strong dependence of the electronic properties of air-exposed GaN surfaces on adsorbates. As a result, we advocate the use of the common cleaning steps analyzed here to re-initialize at will GaN ( 1 1 ¯ 00 ) and (0001) surfaces into pre-defined states.

The electron spin dynamics in spontaneously formed GaN nanowires (NWs) on Si(111) is investigated by time-resolved magneto-optical Kerr-rotation spectroscopy for temperatures from 15 to 260 K. A strong increase in the electron spin relaxation time by more than an order of magnitude is found as compared to bulk GaN. The temperature dependence of spin relaxation is characterized by two regimes, which are explained by a model taking into account the coexistence of two different mechanisms. As a result, the spin lifetime is limited by hyperfine interaction of localized electron spins with nuclear spins at low temperatures. The mesoscopic electron confinement in the NWs leads to a dominance of Dyakonov-Perel spin relaxation driven by interface-induced contributions at high temperatures, resulting in a slow-down, but not complete suppression of spin relaxation as compared to bulk GaN. These findings underline the important role of the high surface-to-volume ratio in NWs.

A comprehensive description of the self-assembled formation of GaN nanowires (NWs) by plasma-assisted molecular beam epitaxy (PAMBE) on amorphous-Al x O y buffered Si is presented. The incubation time that precedes the formation of GaN NWs is analyzed as a function of the growth parameters using line-of-sight quadrupole mass spectrometry. We found that the incubation time follows an Arrhenius-type temperature dependence as well as an inverse power law with respect to the Ga flux. Our results reveal a weaker dependence of the incubation time on the Ga flux and faster nucleation on amorphous-Al x O y in comparison to conventional nitridated Si substrates. In addition, an unprecedented analysis of the dependence of the incubation time on the N flux demonstrates a stronger dependence of the incubation time on the N than on the Ga flux. Our results are summarized in growth diagrams to visualize the impact of the growth parameters on the incubation time. The diagrams can also be used to predict the incubation time for so far unexplored growth conditions. Finally, we measured the desorbing Ga flux upon the nucleation stage to determine the growth parameters that result in effective N-rich conditions as required for the self-assembled formation of GaN NWs. These original measurements were combined with the knowledge gained on the incubation time to create a growth map that illustrates the different growth regimes that can be obtained when GaN is grown on an amorphous-Al x O y buffer layer, regardless of the host substrate. Such a map provides a useful guide to induce the growth and control the morphology of GaN NW ensembles on amorphous-Al x O y . Results presented in this work allow to conclude that amorphous-Al x O y is preferred over nitridated Si as it enables shorter incubation times as well as a wider range of growth parameters to induce the self-assembled formation of GaN NWs in PAMBE.

The composition, strain and surface morphology of (0001)InGaN layers are investigated as a function of growth temperature (460–645 °C) and impinging In flux. Three different growth regimes: nitrogen-rich, metal-rich and intermediate metal-rich, are clearly identified and found to be in correlation with surface morphology and strain relaxation. Best epilayers’ quality is obtained when growing under intermediate metal-rich conditions, with 1–2 monolayers thick In ad-coverage. For a given In flux, the In incorporation decreases with increasing growth temperature due to InN thermal decomposition that follows an Arrhenius behavior with 1.84±0.12 eV activation energy.

We report on plasma-assisted molecular beam epitaxial growth of almost randomly oriented, uniformly tilted, and vertically aligned self-assembled GaN nanowires (NWs), respectively, on different types of polycrystalline Ti foils. The NW orientation with respect to the substrate normal, which is affected by an in situ treatment of the foil surface before NW growth, depends on the crystallinity of the native oxide. Direct growth on the as-received foils results in the formation of ensembles of nearly randomly oriented NWs due to the strong roughening of the surface induced by chemical reactions between the impinging elements and Ti. Surface nitridation preceding the NW growth is found to reduce this roughening by transformation of the uppermost layers into TiN and TiO x N y species. These compounds are more stable against chemical reactions and facilitate the growth of uniformly oriented GaN NW ensembles on the surface of the individual grains of the polycrystalline Ti foils. If an amorphous oxide layer is present at the foil surface, vertically oriented NWs are obtained all across the substrate because this layer blocks the transfering of the epitaxial information from the underlying grains. The control of NW orientation and the understanding behind the achievement of vertically oriented NWs obtained in this study represent an important step towards the realization of GaN NW-based bendable devices on polycrystalline metal foils. Locked until 20.9.2018 due to copyright restrictions. This is an author-created, un-copyedited version of an article accepted for publication/published in [Nanotechnology]. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The Version of Record is available online at http://iopscience.iop.org/article/10.1088/1361-6528/aa84a1/meta

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Appl. Phys. Rev. 3, 041303 (2016) and may be found at https://doi.org/10.1063/1.4963919., The polar nature of the wurtzite crystalline structure of GaN and ZnO results in the existence of a spontaneous electric polarization within these materials and their associated alloys (Ga,Al,In)N and (Zn,Mg,Cd)O. The polarity has also important consequences on the stability of the different crystallographic surfaces, and this becomes especially important when considering epitaxial growth. Furthermore, the internal polarization fields may adversely affect the properties of optoelectronic devices but is also used as a potential advantage for advanced electronic devices. In this article, polarity-related issues in GaN and ZnO are reviewed, going from theoretical considerations to electronic and optoelectronic devices, through thin film, and nanostructure growth. The necessary theoretical background is first introduced and the stability of the cation and anion polarity surfaces is discussed. For assessing the polarity, one has to make use of specific characterization methods, which are described in detail. Subsequently, the nucleation and growth mechanisms of thin films and nanostructures, including nanowires, are presented, reviewing the specific growth conditions that allow controlling the polarity of such objects. Eventually, the demonstrated and/or expected effects of polarity on the properties and performances of optoelectronic and electronic devices are reported. The present review is intended to yield an in-depth view of some of the hot topics related to polarity in GaN and ZnO, a fast growing subject over the last decade.

Growing $I\phantom{\rule{0}{0ex}}I\phantom{\rule{0}{0ex}}I-V$ semiconductor alloys like GaN along different crystal directions, to yield either ``Ga-polar'' or ``N-polar'' structures, can have a profound effect on optoelectronic device properties---in particular, green emission from LEDs. For example, the authors find that N-polar (In,Ga)N/GaN quantum wells do not exhibit any detectable luminescence, in striking contrast to their Ga-polar counterparts. This is due to a high density of nonradiative defects at the interfaces between wells and barriers. These results point away from N-polar systems for further development of long-wavelength LEDs.

We demonstrate the self-assembled growth of vertically aligned GaN nanowire ensembles on a flexible Ti foil by plasma-assisted molecular beam epitaxy. The analysis of single nanowires by transmission electron microscopy reveals that they are single crystalline. Low-temperature photoluminescence spectroscopy demonstrates that, in comparison to standard GaN nanowires grown on Si, the nanowires prepared on the Ti foil exhibit a equivalent crystalline perfection, a higher density of basal-plane stacking faults, but a reduced density of inversion domain boundaries. The room-temperature photoluminescence spectrum of the nanowire ensemble is not influenced or degraded by the bending of the substrate. The present results pave the way for the fabrication of flexible optoelectronic devices based on GaN nanowires on metal foils., 4 pages, 3 figures

We experimentally investigate whether crystal polarity affects the growth of GaN nanowires in plasma-assisted molecular beam epitaxy and whether their formation has to be induced by defects. For this purpose, we prepare smooth and coherently strained AlN layers on 6H-SiC(0001) and SiC(0001̅) substrates to ensure a well-defined polarity and an absence of structural and morphological defects. On N-polar AlN, a homogeneous and dense N-polar GaN nanowire array forms, evidencing that GaN nanowires form spontaneously in the absence of defects. On Al-polar AlN, we do not observe the formation of Ga-polar GaN NWs. Instead, sparse N-polar GaN nanowires grow embedded in a Ga-polar GaN layer. These N-polar GaN nanowires are shown to be accidental in that the necessary polarity inversion is induced by the formation of Si(x)N. The present findings thus demonstrate that spontaneously formed GaN nanowires are irrevocably N-polar. Due to the strong impact of the polarity on the properties of GaN-based devices, these results are not only essential to understand the spontaneous formation of GaN nanowires but also of high technological relevance.

We investigate the formation of the ternary alloy InxGa1–xN in the growth of self-induced nanowires by plasma-assisted molecular beam epitaxy. A series of samples grown at different temperatures were analyzed in situ by line-of-sight quadrupole mass spectrometry, and the predicted composition was verified by X-ray diffraction on as-grown nanowire ensembles. The InxGa1–xN composition is determined by the thermally activated loss of In due to InN decomposition and In desorption, similar to the composition of planar layers. The convolution of decomposition, reincorporation, and desorption is described by an apparent activation energy of about 2.5 eV. We show the feasibility of in situ control of the InxGa1–xN nanowire composition by line-of-sight quadrupole mass spectrometry.

High-resolution monochromated electron energy loss spectroscopy (EELS) at subnanometric spatial resolution and

We investigate the occurrence of interfacial reactions during the self-assembled formation of GaN nanowires on Ti/Al2O3(0001) substrates in plasma-assisted molecular beam epitaxy. The conditions typical for the synthesis of ensembles of long nanowires (>1 μm) are found to promote several chemical reactions. In particular, the high substrate temperature leads to the interdiffusion of Al and O at the Ti/Al2O3 interface resulting in the formation of Al x Ti y O1-x-y and Ti x O1-x compounds. Furthermore, O is found to incorporate into the nanowires degrading their luminescence by heavy n-type doping. At the same time, impinging Ga and N species react with the substrate giving rise to the simultaneous formation of single-crystalline TiN and Ga x Ti y O1-x-y compounds. The latter compounds tend to form hillocks at the substrate surface, on top of which nanowires elongate with large tilt angles with respect to the substrate normal. We develop here a specific process in order to mitigate the detrimental effects of these interfacial reactions, while maintaining the low areal density and absence of coalescence which is the strong asset of growing nanowires on Ti/Al2O3. We find that the combination of a thick Ti film with an intentional low temperature nitridation step preceding nanowire growth and a limited growth temperature results in ensembles of uncoalesced and well-oriented nanowires with luminescence properties comparable to those of standard GaN nanowires prepared on Si. All these properties, together with the inherent benefits of integrating semiconductors on metals, make the present materials combination a promising platform for the further development of group-III nitride nanowire-based devices.

Epilayers of the quaternary alloy AlxInyGa1−x−yN have been grown on GaN/sapphire templates by plasma-assisted molecular beam epitaxy. The emission properties and elemental compositions of these samples were evaluated simultaneously and intercorrelated by combining hyperspectral cathodoluminescence imaging and wavelength-dispersive X-ray mapping. Use was made of inherent variations in growth temperature across a single epilayer to study the resultant effect on the different metal fractions and luminescence emission wavelength. By examining statistical correlations in this data, the interdependence of the fractions of constituent binary compounds, together with the associated changes in emission characteristics, can be clarified without the need to grow a systematic series of samples.

We study the nature of excitons bound to ${I}_{1}$ basal plane stacking faults in ensembles of ultrathin GaN nanowires by continuous-wave and time-resolved photoluminescence spectroscopy. These ultrathin nanowires, obtained by the thermal decomposition of spontaneously formed GaN nanowire ensembles, are tapered and have tip diameters down to 6 nm. With decreasing nanowire diameter, we observe a strong blueshift of the transition originating from the radiative decay of stacking fault-bound excitons. Moreover, the radiative lifetime of this transition in the ultrathin nanowires is independent of temperature up to 60 K and significantly longer than that of the corresponding transition in as-grown nanowires. These findings reveal a zero-dimensional character of the confined exciton state and thus demonstrate that ${I}_{1}$ stacking faults in ultrathin nanowires act as genuine quantum dots.

We investigate the influence of modified growth conditions during the spontaneous formation of GaN nanowires on Si(111) in plasma-assisted molecular beam epitaxy. We find that a two-step growth approach, where the substrate temperature is increased during the nucleation stage, is an efficient method to gain control over the area coverage, average diameter, and coalescence degree of GaN nanowire ensembles. Furthermore, we also demonstrate that the growth conditions employed during the incubation time that precedes nanowire nucleation do not influence the properties of the final nanowire ensemble. Therefore, when growing GaN nanowires at elevated temperatures or with low Ga/N ratios, the total growth time can be reduced significantly by using more favorable growth conditions for nanowire nucleation during the incubation time.

We use line-of-sight quadrupole mass spectrometry to monitor the spontaneous formation of GaN nanowires on Si during molecular beam epitaxy. We find that the temporal evolution of nanowire ensembles is well described by a double logistic function. The analysis of the temporal evolution of nanowire ensembles, prepared under a wide variety of growth conditions, allows us to construct a growth diagram that can be used to predict the average delay time that precedes nanowire formation.

We investigate the origin of the fast recombination dynamics of bound and free excitons in GaN nanowire ensembles by temperature-dependent photoluminescence spectroscopy using both continuous-wave and pulsed excitation. The exciton recombination in the present GaN nanowires is dominated by a nonradiative channel between 10 and 300 K. Furthermore, bound and free excitons in GaN NWs are strongly coupled even at low temperatures resulting in a common lifetime of these states. By solving the rate equations for a coupled two-level system, we show that one cannot, in practice, distinguish whether the nonradiative decay occurs directly via the bound or indirectly via the free state. The nanowire surface and coalescence-induced dislocations appear to be the most obvious candidates for nonradiative defects, and we thus compare the exciton decay times measured for a variety of GaN nanowire ensembles with different surface-to-volume ratio and coalescence degrees. The data are found to exhibit no correlation with either of these parameters, i.e., the dominating nonradiative channel in the GaN nanowires under investigation is neither related to the nanowire surface, nor to coalescence-induced defects. Hence we conclude that nonradiative point defects are the origin of the fast recombination dynamics of excitons in GaN nanowires.

We investigate the structural and optical properties of spontaneously formed GaN nanowires with different degrees of coalescence. This quantity is determined by an analysis of the cross-sectional area and perimeter of the nanowires obtained by plan-view scanning electron microscopy. X-ray diffraction experiments are used to measure the inhomogeneous strain in the nanowire ensembles as well as the orientational distribution of the nanowires. The comparison of the results obtained for GaN nanowire ensembles prepared on bare Si(111) and AlN buffered 6H-SiC(000-1) reveals that the main source of the inhomogeneous strain is the random distortions caused by the coalescence of adjacent nanowires. The magnitude of the strain inhomogeneity induced by nanowire coalescence is found not to be determined solely by the coalescence degree, but also by the mutual misorientation of the coalesced nanowires. The linewidth of the donor-bound exciton transition in photoluminescence spectra does not exhibit a monotonic increase with the coalescence degree. In contrast, the comparison of the root mean square strain with the linewidth of the donor-bound exciton transition reveals a clear correlation: the higher the strain inhomogeneity, the larger the linewidth., 18 pages, 7 figures

We investigate the nature of excitons bound to I1 basal-plane stacking faults [(I1,X)] in GaN nanowire ensembles by continuous-wave and time-resolved photoluminescence spectroscopy. Based on the linear increase of the radiative lifetime of these excitons with temperature, they are demonstrated to exhibit a two-dimensional density of states, i.e., a basal-plane stacking fault acts as a quantum well. From the slope of the linear increase, we determine the oscillator strength of the (I1,X) and show that the value obtained reflects the presence of large internal electrostatic fields across the stacking fault. While the recombination of donor-bound and free excitons in the GaN nanowire ensemble is dominated by nonradiative phenonema already at 10 K, we observe that the (I1,X) recombines purely radiatively up to 60 K. This finding provides important insight into the nonradiative recombination processes in GaN nanowires. First, the radiative lifetime of about 6 ns measured at 60 K sets an upper limit for the surface recombination velocity of 210 cm s −1 considering the nanowires mean diameter of 50 nm. Second, the density of nonradiative centers responsible for the fast decay of donor-bound and free excitons cannot be higher than 6 × 10 16 cm −3 . As a consequence, the nonradiative decay of donor-bound excitons in these GaN nanowire ensembles has to occur indirectly via the free exciton state.

A majority of the point defects in GaN that are responsible for broad photoluminescence (PL) bands remain unidentified. One of them is the green luminescence band (GL2) having a maximum at 2.35 eV which was observed previously in undoped GaN grown by molecular-beam epitaxy in Ga-rich conditions. The same PL band was observed in Mg-doped GaN, also grown in very Ga-rich conditions. The unique properties of the GL2 band allowed us to reliably identify it in different samples. The best candidate for the defect which causes the GL2 band is a nitrogen vacancy $({V}_{\mathrm{N}})$. We propose that transitions of electrons from the conduction band to the +/2+ transition level of the ${V}_{\mathrm{N}}$ defect are responsible for the GL2 band in high-resistivity undoped and Mg-doped GaN.

We observe unusually narrow donor-bound exciton transitions (0.4 meV) in the photoluminescence spectra of GaN nanowire ensembles grown on Si(111) substrates at very high (> 850 degrees Celsius) temperatures. The spectra of these samples reveal a prominent transition of excitons bound to neutral Si impurities which is not observed for samples grown under standard conditions. Motivated by these experimental results, we investigate theoretically the impact of surface-induced internal electric fields on the binding energy of donors by a combined Monte Carlo and envelope function approach. We obtain the ranges of doping and diameter for which the potential is well described using the Poisson equation, where one assumes a spatially homogeneous distribution of dopants. Our calculations also show that surface donors in nanowires with a diameter smaller than 100 nm are ionized when the surface electric field is larger than about 10 kV/cm, corresponding to a doping level higher than 2 x 10^16 cm^-3. This result explains the experimental observation: since the (D+,X) complex is not stable in GaN, surface-donor-bound excitons do not contribute to the photoluminescence spectra of GaN nanowires above a certain doping level, and the linewidth reflects the actual structural perfection of the nanowire ensemble.

AlN layers with thicknesses between 2 and 14 nm were grown on Si(111) substrates by molecular beam epitaxy. The effect of the AlN layer thickness on the morphology and nucleation time of spontaneously formed GaN nanowires (NWs) was investigated by scanning electron microscopy and line-of-sight quadrupole mass spectrometry, respectively. We observed that the alignment of the NWs grown on these layers improves with increasing layer thickness while their nucleation time decreases. Our results show that 4 nm is the smallest thickness of the AlN layer that allows the growth of well-aligned NWs with short nucleation time. Such an AlN buffer layer was successfully employed, together with a patterned SiOx mask, for the selective-area growth (SAG) of vertical GaN NWs. In addition, we fabricated light-emitting diodes (LEDs) from NW ensembles that were grown by means of self-organization phenomena on bare and on AlN-buffered Si substrates. A careful characterization of the optoelectronic properties of the two devices showed that the performance of NW-LEDs on bare and AlN-buffered Si is similar. Electrical conduction across the AlN buffer is facilitated by a high number of grain boundaries that were revealed by transmission electron microscopy. These results demonstrate that grainy AlN buffer layers on Si are compatible both with the SAG of GaN NWs and LED operation. Therefore, this study is a first step towards the fabrication of LEDs on Si substrates based on homogeneous NW ensembles., Comment: 12 pages, 6 figures