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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.

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

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.

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.

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.

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.

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.

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 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.

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.

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

We investigate the axial and radial growth of GaN nanowires upon a variation of the Ga flux during molecular beam epitaxial growth. An increase in the Ga flux promotes radial growth without affecting the axial growth rate. In contrast, a decrease in the Ga flux reduces the axial growth rate without any change in the radius. These results are explained by a kinetic growth model that accounts for both the diffusion of Ga adatoms along the side facets toward the nanowire tip and the finite amount of active N available for the growth. The model explains the formation of a new equilibrium nanowire radius after increasing the Ga flux and provides an explanation for two well-known but so far not understood experimental facts: the necessity of effectively N-rich conditions for the spontaneous growth of GaN nanowires and the increase in nanowire radius with increasing III/V flux ratio.

We present a comprehensive description of the self-assembled nucleation and growth of GaN nanowires (NWs) by plasma-assisted molecular beam epitaxy on amorphous Al x O y buffers (a-Al x O y ) prepared by atomic layer deposition. The results are compared with those obtained on nitridated Si(111). Using line-of-sight quadrupole mass spectrometry, we analyze in situ the incorporation of Ga starting from the incubation and nucleation stages till the formation of the final nanowire ensemble and observe qualitatively the same time dependence for the two types of substrates. However, on a-Al x O y the incubation time is shorter and the nucleation faster than on nitridated Si. Moreover, on a-Al x O y we observe a novel effect of decrease in incorporated Ga flux for long growth durations which we explain by coalescence of NWs leading to reduction of the GaN surface area where Ga may reside. Dedicated samples are used to analyze the evolution of surface morphology. In particular, no GaN nuclei are detected when growth is interrupted during the incubation stage. Moreover, for a-Al x O y , the same shape transition from spherical cap-shaped GaN crystallites to the NW-like geometry is found as it is known for nitridated Si. However, while the critical radius for this transition is only slightly larger for a-Al x O y than for nitridated Si, the critical height is more than six times larger for a-Al x O y . Finally, we observe that in fully developed NW ensembles, the substrate no longer influences growth kinetics and the same N-limited axial growth rate is measured on both substrates. We conclude that the same nucleation and growth processes take place on a-Al x O y as on nitridated Si and that these processes are of a general nature. Quantitatively, nucleation proceeds somewhat differently, which indicates the influence of the substrate, but once shadowing limits growth processes to the upper part of the NW ensemble, they are not affected anymore by the type of substrate.

International audience; Low-temperature photoluminescence is studied in detail in GaN nanocolumns NCs grown by plasma-assisted molecular beam epitaxy under various conditions substrate temperature and impinging Ga/N flux ratio . The relative intensities of the different emission lines, in particular those related to structural defects, appear to be correlated with the growth conditions, and clearly linked to the NC sample morphology. We demonstrate, in particular, that all lines comprised between 3.10 and 3.42 eV rapidly lose intensity when the growth conditions are such that the NC coalescence is reduced. The well-known line around 3.45 eV, characteristic of GaN NC samples, shows, however, a behavior that is exactly the opposite of the other lines, namely, for growth conditions leading to reduced NC coalescence, this line tends to become more prominent, thus proving to be intrinsic to individual GaN NCs.

The influence of the substrate temperature, III/V flux ratio, and mask geometry on the selective area growth of GaN nanocolumns is investigated. For a given set of growth conditions, the mask design (diameter and pitch of the nanoholes) is found to be crucial to achieve selective growth within the nanoholes. The local III/V flux ratio within these nanoholes is a key factor that can be tuned, either by modifying the growth conditions or the mask geometry. On the other hand, some specific growth conditions may lead to selective growth but not be suitable for subsequent vertical growth. With optimized conditions, ordered GaN nanocolumns can be grown with a wide variety of diameters. In this work, ordered GaN nanocolumns with diameter as small as 50 nm are shown.

We report on properties of high quality ~60 nm thick InAlN layers nearly in-plane lattice-matched to GaN, grown on c-plane GaN-on-sapphire templates by plasma-assisted molecular beam epitaxy. Excellent crystalline quality and low surface roughness are confirmed by X-ray diffraction, transmission electron microscopy, and atomic force microscopy. High annular dark field observations reveal a periodic in-plane indium content variation (8 nm period), whereas optical measurements evidence certain residual absorption below the band-gap. The indium fluctuation is estimated to be +/- 1.2% around the nominal 17% indium content via plasmon energy oscillations assessed by electron energy loss spectroscopy with sub-nanometric spatial resolution.

This work reports on the growth by molecular beam epitaxy and characterization of InN/InGaN multiple quantum wells (MQWs) emitting at 1.5 μm. X-ray diffraction (XRD) spectra show satellite peaks up to the second order. Estimated values of well (3 nm) and barrier (9 nm) thicknesses were derived from transmission electron microscopy and the fit between experimental data and simulated XRD spectra. Transmission electron microscopy and XRD simulations also confirmed that the InGaN barriers are relaxed with respect to the GaN template, while the InN MQWs grew under biaxial compression on the InGaN barriers. Low temperature (14 K) photoluminescence measurements reveal an emission from the InN MQWs at 1.5 μm. Measurements as a function of temperature indicate the existence of localized states, probably due to InN quantum wells’ thickness fluctuations as observed by transmission electron microscopy.

This work reports on the fabrication of Schottky barrier based Mg-doped (In,Ga)N layers for fluorescence applications. Mg acceptors are used in order to compensate surface and bulk donors that prevent the fabrication of Schottky contacts on unintentionally doped (In,Ga)N layers grown by plasma-assisted molecular beam epitaxy (PA-MBE). Rectifying properties of the contacts exhibited a major improvement when (In,Ga)N : Mg was used. The electrical and optical measurements of the layers showed a hole concentration of up to 3 × 1019 holes cm−3 with a Mg acceptor activation energy of ∼60 meV. Back-illuminated photodiodes fabricated on 800 nm thick Mg-doped In0.18Ga0.82N layers exhibited a band pass photo-response with a rejection ratio >102 between 420 and 470 nm and peak responsivities of 87 mA W−1 at ∼470 nm. The suitability of these photodiodes for fluorescence measurements was demonstrated.

We demonstrate six to ten period lattice-matched In0.18Al0.82N/GaN distributed Bragg reflectors with peak reflectivity centred around 400 nm, grown by molecular beam epitaxy. Thanks to the well-tuned ternary alloy composition crack-free layers have been obtained as confirmed by both optical and scanning electron microscopy. In addition, cross-sectional analysis by high resolution transmission electron microscopy reveals highly periodic structure with abrupt interfaces. When the number of DBRs periods increased from six to ten, peak reflectivity increased from 45% to 60%. This increase was found to be in reasonable agreement with theoretical simulations. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Indium incorporation and surface morphology of InAlN layers grown on (0001) GaN by plasma-assisted molecular beam epitaxy were investigated as a function of the impinging In flux and the substrate temperature in the 450–610 °C range. In incorporation was found to decrease with substrate temperature due to thermal decomposition of the growing layer, while for a given temperature it increased with the impinging In flux until stoichiometry was reached at the growth front. The InN losses during growth followed an Arrhenius behavior characterized by an activation energy of 2.0 eV. A growth diagram highly instrumental to identify optimum growth conditions was established.

Indium incorporation into wurtzite (0001)-oriented InxAlyGa1−x−yN layers grown by plasma-assisted molecular beam epitaxy was studied as a function of the growth temperature (565–635 °C) and the AlN mole fraction (0.01

A study of the GaN nanocolumns nucleation and growth by molecular beam epitaxy on Si(111) is presented. Ga droplets with different diameters (340-90 nm) were deposited on the substrate. prior to growth, to determine any effect on the nanocolumns size and distribution. Results indicate that there is no difference in nanocolumnar size and density whether Ga droplets are used or not, meaning that Ga droplets do not act as catalysts for the nanocolumns nucleation. In addition, Ga droplets were never observed on the nanocolumn tips upon growth termination. These findings rule out the vapor-liquid-solid mechanism, Instead, driven by a strong lattice mismatch nanocolumnar nucleation occurs spontaneously by Volmer-Weber growth mechanism, whereas nitrogen excess prevents the nucleation sites coalescence. Further nanocolumnar growth proceeds by direct Ga incorporation on the nanocolumns top and by Ga diffusion along the nanocolumns sidewalls up to their apex. Related to this diffusion mechanism, we found that Ga droplets, when used, may act as reservoirs to feed Ga atoms to the neighboring nanocolumns. Nanocolumns preserve a constant diameter if growth conditions are not modified because of a strong metal ad-atom diffusion length along their sidewalls. The effect of using AIN buffer layers on the nanocolumnar growth and morphology is also addressed. (C) 2008 Elsevier B.V. All rights reserved.

The growth conditions to achieve group-III-nitride nanocolumns and nanocolumnar heterostructures by plasma-assisted molecular beam epitaxy are studied. The evolution of the nanocolumnar morphology with the growth conditions is determined for (Ga,Al)N and (In,Ga)N nanocolumns. The mechanisms behind the nanocolumnar growth under high N-rich conditions are clarified in the sense that no seeding or catalysts are required, as it is the case in the vapour-liquid-solid model that applies to most nanocolumns grown by metal organic chemical vapour deposition, either with group-III nitrides, II–VI or III–V compounds. Some examples of nanocolumnar heterostructures are given, like quantum disks and cylindrical nanocavities. Preliminary results on the growth of arrays of ordered GaN nanocolumns are reported. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Carrier confinement effects in nanocolumnar ${\mathrm{Al}}_{x}{\mathrm{Ga}}_{1\ensuremath{-}x}\mathrm{N}∕\mathrm{Ga}\mathrm{N}$ multiple quantum disks have been studied by photoluminescence, as a function of the Al content and quantum disk thickness. Experimental emission energies are compared to theoretical calculations based on a one-dimensional Schr\"odinger-Poisson solver, including spontaneous and piezoelectric polarizations, surface potentials, and strain. An inhomogeneous biaxial (in-plane) strain distribution within the GaN quantum disks, pseudomorphically grown on strain-free ${\mathrm{Al}}_{x}{\mathrm{Ga}}_{1\ensuremath{-}x}\mathrm{N}$ nanocolumns, results from a reduction of the accumulated elastic energy at the disk free surface (GaN-air boundary). This strain reduction annihilates partially the piezoelectric field, giving rise to a specific carrier confinement mechanism (strain confinement), that depends on the disk thickness. This strain confinement mechanism is the origin of the luminescence quenching in very thin GaN quantum disks, as well as the main source of the emission linewidth broadening.

Self-assembled columnar $\mathrm{AlGaN}/\mathrm{GaN}$ nanocavities, with an active region of GaN quantum disks embedded in an AlGaN nanocolumn and cladded by top and bottom $\mathrm{AlN}/\mathrm{GaN}$ Bragg mirrors, were grown. The nanocavity has no cracks or extended defects, due to the relaxation at the Si interface and to the nanocolumn free-surface to volume ratio. The emission from the active region matched the peak reflectivity by tuning the Al content and the GaN disks thickness. Quantum confinement effects that depend on both the disk thickness and the inhomogeneous strain distribution within the disks are clearly observed.

The successful growth of AlGaN nanocolumns by plasma assisted MBE, with different Al compositions, opened the way for achieving nano-heterostructures including GaN Quantum Discs (QDss). The luminescence emission from the QDss embedded in the AlGaN nanocolumns was tuned by changing their thickness and/or the Al composition of the barriers. Such a nano-heterostructure was then enclosed between two AlN/GaN Distributed Bragg Reflectors (DBR), with nominal reflectivities of 90 and 50%. The choice of the AlN/GaN bilayers for the DBRs allowed to reach these reflectivity values with a significantly lower number of periods, as compared to the AlGaN/GaN stacks. The resulting nanocavity has been characterized by cathodoluminescence (CL), and Scanning and Transmission Electron Microscopy (SEM, TEM). CL measurements show that the emission from the nanocavity is quite close to the targeted value. TEM data points to the need of optimized conditions to grow AlN columnar layers in order to avoid the lateral overgrowth in the columnar nanostructure.

We investigate GaN nanowire ensembles spontaneously formed in plasma-assisted molecular beam epitaxy by non-destructive low-energy electron diffraction (LEED) and x-ray photoelectron diffraction (XPD). We show that GaN nanowire ensembles prepared on AlN-buffered 6H-SiC(0001¯) substrates with well-defined N polarity exhibit similar LEED intensity-voltage curves and angular distribution of photo-emitted electrons as N-polar free-standing GaN layers. Therefore, as in the case of GaN layers, LEED and XPD are found to be suitable techniques to assess the polarity of GaN nanowire ensembles on a macroscopic scale. The analysis of GaN nanowire ensembles prepared on bare Si(111) allows us to conclude that, on this non-polar substrate, the majority of nanowires is also N-polar.

We analyze the properties of Fe Schottky contacts prepared in situ on n-type GaN(0001) by molecular beam epitaxy. In particular, we investigate the suitability of these epitaxial Fe layers for electrical spin injection. Current-voltage-temperature measurements demonstrate pure field emission for Fe/GaN:Si Schottky diodes with [Si]=5×1018 cm−3. The Schottky barrier height of the clean, epitaxial Fe/GaN interface is determined by both current-voltage-temperature and capacitance-voltage techniques to be (1.47±0.09)eV.

We report on molecular beam epitaxy growth and characterization of ten-period lattice-matched InAlN/GaN distributed Bragg reflectors (DBRs), with peak reflectivity centered around 400 nm. Thanks to the well tuned ternary alloy composition, crack-free surfaces have been obtained, as confirmed by both optical and transmission electron microscopy (TEM). Their good periodicity and well-defined interfaces have been confirmed by both x-ray diffraction and TEM measurements. Peak reflectivity values as high as 60% with stop bands of 30 nm have been demonstrated. Optical measurements revealed that discrepancy between the obtained (60%) and the theoretically expected (∼75%) reflectivity is a consequence of significant residual absorption (∼35%). TEM measurements revealed the coexistence of zinc-blende and wurtzite phases, as well as planar defects, mainly in GaN. These defects are suggested as the potential source of the undesired absorption and/or scattering effects that lowered the DBRs’ peak reflectivity.

The morphology of GaN samples grown by plasma-assisted molecular beam epitaxy on Si(111) was systematically studied as a function of impinging Ga/N flux ratio and growth temperature (730–850 °C). Two different growth regimes were identified: compact and nanocolumnar. A growth diagram was established as a function of growth parameters, exhibiting the transition between growth regimes, and showing under which growth conditions GaN cannot be grown due to thermal decomposition and Ga desorption. Present results indicate that adatoms diffusion length and the actual Ga/N ratio on the growing surface are key factors to achieve nanocolumnar growth.

Thermal decomposition of wurtzite (0001)-oriented GaN was analyzed: in vacuum, under active N exposure, and during growth by rf plasma-assisted molecular beam epitaxy. The GaN decomposition rate was determined by measurements of the Ga desorption using in situ quadrupole mass spectrometry, which showed Arrhenius behavior with an apparent activation energy of 3.1 eV. Clear signatures of intensity oscillations during reflection high-energy electron diffraction measurements facilitated complementary evaluation of the decomposition rate and highlighted a layer-by-layer decomposition mode in vacuum. Exposure to active nitrogen, either under vacuum or during growth under N-rich growth conditions, strongly reduced the GaN losses due to GaN decomposition.

Room temperature photoluminescence and optical absorption spectra have been measured in wurtzite InxAlyGa1−x−yN (x ∼ 0.06, 0.02

A study of AlInGaN epilayers, grown by plasma-assisted molecular beam epitaxy, was performed using spatially resolved x-ray microanalysis and luminescence spectroscopy in order to investigate competition between the incorporation of In, Al, and Ga as a function of the growth temperature in the 565-660 °C range and the nominal AlN mole fraction. The samples studied have AlN and InN mole fractions in the ranges of 4%-30% and 0%-16%, respectively. Composition measurements show the effect of decreasing temperature to be an increase in the incorporation of InN, accompanied by a small but discernible decrease in the ratio of GaN to AlN mole fractions. The incorporation of In is also shown to be significantly increased by decreasing the Al mole fraction. Optical emission peaks, observed by cathodoluminescence mapping and by photoluminescence, provide further information on the epilayer compositions as a function of substrate temperature, and the dependencies of peak energy and linewidth are plotted.