Search

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$^{\circ}$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 behaviour characterized by an activation energy of 2.0 eV. A growth diagram highly instrumental to identify optimum growth conditions was established.

Real-time analysis of the growth modes during homoepitaxial (0001)GaN growth by plasma-assisted molecular beam epitaxy was performed using reflection high energy electron diffraction. A growth mode map was established as a function of Ga/N flux ratio and growth temperature, exhibiting distinct transitions between three-dimensional (3D), layer-by-layer and step-flow growth mode. The layer-by-layer to step-flow growth transition under Ga-rich growth was surfactant mediated and related to a Ga adlayer coverage of one monolayer. Under N-rich conditions the transition from 3D to layer-by-layer growth was predominantly thermally activated, facilitating two-dimensional growth at temperatures of thermal decomposition.

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.

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 unconventional growth approaches to minimize the incubation time and thus facilitate significantly higher growth temperatures (up to 875$^{\circ}$C). We achieve this by: (i) using III/V flux ratios larger than one 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 and the low-temperature photoluminescence spectra are comparable to those of state-of-the-art free-standing GaN layers grown by hydride vapor phase epitaxy.

Room temperature photoluminescence and optical absorption spectra have been measured in wurtzite In$_{x}$Al$_{y}$Ga$_{1-x-y}$N (x $\approx$ 0.06, 0.02 < y < 0.27) layers grown by molecular beam epitaxy. Photoluminescence spectra show both an enhancement of the integrated intensity and an increasing Stokes shift with the Al content. Both effects arise from an Al-enhanced exciton localization revealed by the S- and W-shaped temperature dependences of the photoluminescence emission energy and bandwidth respectively. Present results point to these materials as a promising choice for the active region in efficient light emitters. An In-related bowing parameter of 1.6 eV was derived from optical absorption data.

Indium incorporation into wurtzite (0001)-oriented In$_{x}$Al$_{y}$Ga$_{1-x-y}$N layers grown by plasma-assisted molecular beam epitaxy was studied as a function of the growth temperature (565-635 $^{\circ}$C) and the AlN mole fraction (0.01 < y < 0.27). The layer stoichiometry was determined by Rutherford backscattering spectrometry (RBS). RBS shows that Indium incorporation decreased continuously with increasing growth temperature due to thermally enhanced dissociation of In-N bonds and for increasing AlN mole fractions. High resolution x-ray diffraction and transmission electron microscopy (TEM) measurements did not show evidence of phase separation. The mosaicity of the quaternary layers was found to be mainly determined by the growth temperature and independent on alloy composition within the range studied. However, depending on the AlN mole fraction, nanometer-sized composition fluctuations were detected by TEM. Photoluminescence spectra showed a single broad emission at room temperature, with energy and bandwidth S- and W-shaped temperature dependences typical of exciton localization by alloy inhomogeneities. Cathodo-luminescence measurements demonstrated that the alloy inhomogeneities, responsible of exciton localization, occur on a lateral length scale below 150 nm, which is corroborated by TEM.

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 (750-850{\deg}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., Comment: 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 (citation of published article) and may be found at J. Appl. Phys. 106, 126102 (2009) and may be found at https://doi.org/10.1063/1.3267151

We investigated the chemical beam epitaxy of GaP1-xNx to correlate the growth parameters with their properties when they are grown on nominally (001)-oriented Si substrates, as desired for the lattice-matched integration of optoelectronic devices with the standard Si technology. The growth mode as well as the chemical, morphological and structural properties of samples prepared using different growth temperatures and N precursor fluxes were analyzed by RHEED, XRD, RBS, NRA, EDX spectroscopy, AFM and TEM. Our results show that, up to x = 0.04, it is possible to synthesize smooth and chemically homogeneous GaP1-xNx layers with a high-structural quality in a 2D fashion, namely, layer-by-layer. For a given N mole fraction, the layer-by-layer growth mode is favored by lowering the growth temperature while decreasing the N precursor flux. As the flux of the N precursor is increased at a given temperature to enhance N incorporation, the quality of the layers degrades upon exceeding a temperature-dependent threshold; above this threshold, the growing layer experiences a growth mode transition from 2D to 3D after reaching a critical thickness of a few nm. Following that transition, the morphology and the chemical composition become modulated along the [110] direction with a period of several tens of nm. The surface morphology is then characterized by the formation of {113}-faceted wires, while the N concentration is enhanced at the troughs formed in between adjacent (113) and (-1-13) facets. We conclude on the feasibility of fabricating homogeneous thick GaP1-xNx layers lattice matched to Si (x = 0.021) or even with N content up to x=0.04. The possibility of exceeding a N mole fraction of 0.04 without inducing coupled morphological-compositional modulations has also been demonstrated when the layer thickness is kept below the critical value for the 2D-3D growth mode transition.

A wide range of n- and p-type doping levels in GaAs layers grown by chemical beam epitaxy is achieved using H$_{2}$-diluted DTBSi and CBr$_{4}$ as gas precursors for Si and C. We show that the doping level can be varied by modifying either the concentration or the flux of the diluted precursor. Specifically, we demonstrate carrier concentrations of 6$\times$10$^{17}$-1.2$\times$10$^{19}$ cm$^{-3}$ for Si, and 9$\times$10$^{16}$-3.7$\times$10$^{20}$ cm$^{-3}$ for C, as determined by Hall effect measurements. The incorporation of Si and C as a function of the flux of the corresponding diluted precursor is found to follow, respectively, a first and a fourth order power law. The dependence of the electron and hole mobility values on the carrier concentration as well as the analysis of the layers by low-temperature (12 K) photoluminescence spectroscopy indicate that the use of H$_{2}$ for diluting DTBSi or CBr$_{4}$ has no effect on the electrical and optical properties of GaAs.

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.

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 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/Al$_{2}$O$_{3}(0001)$ 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 $f_{x}$ and $f_{z}$ of the air-exposed GaN$\{1\bar100\}$ planes that constitute the nanowire sidewalls are determined experimentally to be 2.25 and $-0.7$~N/m, respectively., Comment: 22 pages, 8 figures

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 ${\deg}C$ enabled by the use of thermally stable TiN$_x$/Al$_2$O$_3$ 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.

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., Comment: 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 study the nature of excitons bound to I1 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 blue shift 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 I1 stacking faults in ultrathin nanowires act as genuine quantum dots.

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., Comment: 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 450 cm/s considering the nanowires mean diameter of 105 nm. Second, the density of nonradiative centers responsible for the fast decay of donor-bound and free excitons cannot be higher than 2x10^16 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.