(In, Ga) alloy droplets are used to catalyse the growth of (In, Ga)As nanowires by molecular beam epitaxy on Si(111) substrates. The composition, morphology and optical properties of these nanowires can be tuned by the employed elemental fluxes. To incorporate more than 10% of In, a high In/(In+Ga) flux ratio above 0.7 is required. We report a maximum In content of almost 30% in bulk (In, Ga)As nanowires for an In/(In+Ga) flux ratio of 0.8. However, with increasing In/(In+Ga) flux ratio, the nanowire length and diameter are notably reduced. Using photoluminescence and cathodoluminescence spectroscopy on nanowires covered by a passivating (In, Al)As shell, two luminescence bands are observed. A significant segment of the nanowires shows homogeneous emission, with a wavelength corresponding to the In content in this segment, while the consumption of the catalyst droplet leads to a spectrally-shifted emission band at the top of the nanowires. The (In,Ga)As nanowires studied in this work provide a new approach for the integration of infrared emitters on Si platforms.
We study the molecular beam epitaxy of AlN nanowires between 950 °C and 1215 °C, well above the usual growth temperatures, to identify optimal growth conditions. The nanowires are grown by self-assembly on TiN(111) films sputtered onto Al2O3. Above 1100 °C, the TiN film is seen to undergo grain growth and its surface exhibits {111} facets where AlN nucleation preferentially occurs. Modeling of the nanowire elongation rate measured at different temperatures shows that the Al adatom diffusion length maximizes at 1150 °C, which appears to be the optimum growth temperature. However, analysis of the nanowire luminescence shows a steep increase in the deep-level signal already above 1050 °C, associated with O incorporation from the Al2O3substrate. Comparison with AlN nanowires grown on Si, MgO and SiC substrates suggests that heavy doping of Si and O by interdiffusion from the TiN/substrate interface increases the nanowire internal quantum efficiency, presumably due to the formation of a SiNxor AlOxpassivation shell. The outdiffusion of Si and O would also cause the formation of the inversion domains observed in the nanowires. It follows that for optoelectronic and piezoelectric applications, optimal AlN nanowire ensembles should be prepared at 1150 °C on TiN/SiC substrates and will require anex situsurface passivation.
The self-assembly of heteroepitaxial GaN nanowires using either molecular beam epitaxy (MBE) or metal-organic vapor phase epitaxy (MOVPE) mostly results in wafer-scale ensembles with ultrahigh (>10µm-2) or ultralow (<1µm-2) densities, respectively. A simple means to tune the density of well-developed nanowire ensembles between these two extremes is generally lacking. Here, we examine the self-assembly of SiNxpatches on TiN(111) substrates which are eventually acting as seeds for the growth of GaN nanowires. We first found that if prepared by reactive sputtering, the TiN surface is characterized by {100} facets for which the GaN incubation time is extremely long. Fast GaN nucleation is only obtained after deposition of a sub-monolayer of SiNxatoms prior to the GaN growth. By varying the amount of pre-deposited SiNx, the GaN nanowire density could be tuned by three orders of magnitude with excellent uniformity over the entire wafer, bridging the density regimes conventionally attainable by direct self-assembly with MBE or MOVPE. The analysis of the nanowire morphology agrees with a nucleation of the GaN nanowires on nanometric SiNxpatches. The photoluminescence analysis of single freestanding GaN nanowires reveals a band edge luminescence dominated by excitonic transitions that are broad and blue shifted compared to bulk GaN, an effect that is related to the small nanowire diameter and to the presence of a thick native oxide. The approach developed here can be principally used for tuning the density of most III-V semiconductors nucleus grown on inert surfaces like 2D materials.
Gallium , Nanowires , Nanowires/chemistry , Tin , Gallium/chemistry , Luminescence , Oxides
We introduce a facile route for the top-down fabrication of ordered arrays of GaN nanowires with aspect ratios exceeding 10 and diameters below 20 nm. Highly uniform thin GaN nanowires are first obtained by lithographic patterning a bilayer Ni/SiNxhard mask, followed by a combination of dry and wet etching in KOH. The SiNxis found to work as an etch stop during wet etching, which eases reproducibility. Arrays with nanowire diameters down to (33 ± 5) nm can be achieved with a uniformity suitable for photonic applications. Next, a scheme for digital etching is demonstrated to further reduce the nanowire diameter down to 5 nm. However, nanowire breaking or bundling is observed for diameters below ≈20 nm, an effect that is associated to capillary forces acting on the nanowires during sample drying in air. Explicit calculations of the nanowire buckling states under capillary forces indicate that nanowire breaking is favored by the incomplete wetting of water on the substrate surface during drying. The observation of intense nanowire photoluminescence at room-temperature indicates good compatibility of the fabrication route with optoelectronic applications. The process can be principally applied to any GaN/SiNxnanostructures and allows regrowth after removal of the SiNxmask.
We report on the direct correlation between the structural and optical properties of single, as-grown core-multi-shell GaAs/In0.15Ga0.85As/GaAs/AlAs/GaAs nanowires. Fabricated by molecular beam epitaxy on a pre-patterned Si(111) substrate, on a row of well separated nucleation sites, it was possible to access individual nanowires in the as-grown geometry. The polytype distribution along the growth axis of the nanowires was revealed by synchrotron-based nanoprobe x-ray diffraction techniques monitoring the axial 111 Bragg reflection. For the same nanowires, the spatially-resolved emission properties were obtained by cathodoluminescence hyperspectral linescans in a scanning electron microscope. Correlating both measurements, we reveal a blueshift of the shell quantum well emission energy combined with an increased emission intensity for segments exhibiting a mixed structure of alternating wurtzite and zincblende stacking compared with the pure crystal polytypes. The presence of this mixed structure was independently confirmed by cross-sectional transmission electron microscopy.
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 light 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.
Optical properties of GaN nanowires (NWs) grown on chemical vapor deposited-graphene transferred on an amorphous support are reported. The growth temperature was optimized to achieve a high NW density with a perfect selectivity with respect to a SiO2 surface. The growth temperature window was found to be rather narrow (815°C ± 5°C). Steady-state and time-resolved photoluminescence from GaN NWs grown on graphene was compared with the results for GaN NWs grown on conventional substrates within the same molecular beam epitaxy reactor showing a comparable optical quality for different substrates. Growth at temperatures above 820 °C led to a strong NW density reduction accompanied with a diameter narrowing. This morphology change leads to a spectral blueshift of the donor-bound exciton emission line due to either surface stress or dielectric confinement. Graphene multi-layered micro-domains were explored as a way to arrange GaN NWs in a hollow hexagonal pattern. The NWs grown on these domains show a luminescence spectral linewidth as low as 0.28 meV (close to the set-up resolution limit).
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.
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.
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.
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.
In this work we study how the multi-element nature of light emitting diodes (LEDs) based on nanowire (NW) ensembles influences their current voltage (I-V) characteristics. We systematically address critical issues of the fabrication process that can result in significant fluctuations of the electrical properties among the individual NWs in such LEDs, paying particular attention to the planarization step. Electroluminescence (EL) maps acquired for two nominally identical NW-LEDs reveal that small processing variations can result in a large difference in the number of individual nano-devices emitting EL. The lower number of EL spots in one of the LEDs is caused by its inhomogeneous electrical properties. The I-V characteristics of this LED cannot be described well by the classical Shockley model. We are able to take into account the multi-element nature of such LEDs and fit the I-V characteristics in the forward bias regime by employing an ad hoc adjusted version of the Shockley equation. More specifically, we introduce a bias dependence of the ideality factor. The basic considerations of our model should remain valid also for other types of devices based on ensembles of interconnected p-n junctions with inhomogeneous electrical properties, regardless of the employed material system.
We investigate the influence of modified growth conditions during the spontaneous formation of GaN nanowires (NWs) 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 NW 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 NWs 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.
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.
Gallium/chemistry , Nanowires/chemistry , Silicon/chemistry , Titanium/chemistry , Nanowires/ultrastructure
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.
InAs segments were grown on top of GaAs islands, initially created by droplet epitaxy on silicon substrate. We systematically explored the growth-parameter space for the deposition of InAs, identifying the conditions for the selective growth on GaAs and for purely axial growth. The axial InAs segments were formed with their sidewalls rotated by 30° compared to the GaAs base islands underneath. Synchrotron X-ray diffraction experiments revealed that the InAs segments are grown relaxed on top of GaAs, with a predominantly zincblende crystal structure and stacking faults.
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(0001) 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.
The oscillating piezoelectric fields accompanying surface acoustic waves are able to transport charge carriers in semiconductor heterostructures. Here, we demonstrate high-frequency (above 1 GHz) acoustic charge transport in GaAs-based nanowires deposited on a piezoelectric substrate. The short wavelength of the acoustic modulation, smaller than the length of the nanowire, allows the trapping of photo-generated electrons and holes at the spatially separated energy minima and maxima of conduction and valence bands, respectively, and their transport along the nanowire with a well defined acoustic velocity towards indium-doped recombination centers.
Nuclear spin hyperpolarization is essential to future solid-state quantum computation using nuclear spin qubits and in highly sensitive magnetic resonance imaging. Though efficient dynamic nuclear polarization in semiconductors has been demonstrated at low temperatures for decades, its realization at room temperature is largely lacking. Here we demonstrate that a combined effect of efficient spin-dependent recombination and hyperfine coupling can facilitate strong dynamic nuclear polarization of a defect atom in a semiconductor at room temperature. We provide direct evidence that a sizeable nuclear field (~150 Gauss) and nuclear spin polarization (~15%) sensed by conduction electrons in GaNAs originates from dynamic nuclear polarization of a Ga interstitial defect. We further show that the dynamic nuclear polarization process is remarkably fast and is completed in <5 µs at room temperature. The proposed new concept could pave a way to overcome a major obstacle in achieving strong dynamic nuclear polarization at room temperature, desirable for practical device applications.
