ScN/GaN(11Ì 00): A New Platform for the Epitaxy of Twin-Free Metal-Semiconductor Heterostructures.

We study the molecular beam epitaxy of rock-salt ScN on the wurtzite GaN(11̅00) surface. To this end, ScN is grown on freestanding GaN(11̅00) substrates and self-assembled GaN nanowires exhibiting (11̅00) sidewalls. On both substrates, ScN crystallizes twin-free thanks to a specific epitaxial relationship, namely ScN(110)[001]∥GaN(11̅00)[0001], providing a congruent, low-symmetry interface. The 13.1% uniaxial lattice mismatch occurring in this orientation mostly relaxes within the first few monolayers of growth by forming a near-coincidence site lattice, where 7 GaN planes coincide with 8 ScN planes, leaving the ScN surface nearly free of extended defects. Overgrowth of the ScN with GaN leads to a kinetic stabilization of the zinc blende phase, that rapidly develops wurtzite inclusions nucleating on {111} nanofacets, commonly observed during zinc blende GaN growth. Our ScN/GaN(11̅00) platform opens a new route for the epitaxy of twin-free metal-semiconductor heterostructures including closely lattice-matched GaN, ScN, HfN, and ZrN compounds.

Uniform large-area surface patterning achieved by metal dewetting for the top-down fabrication of GaN nanowire ensembles.

The dewetting of thin Pt films on different surfaces is investigated as a means to provide the patterning for the top-down fabrication of GaN nanowire ensembles. The transformation from a thin film to an ensemble of nanoislands upon annealing proceeds in good agreement with the void growth model. With increasing annealing duration, the size and shape uniformity of the nanoislands improves. This improvement speeds up for higher annealing temperature. After an optimum annealing duration, the size uniformity deteriorates due to the coalescence of neighboring islands. By changing the Pt film thickness, the nanoisland diameter and density can be quantitatively controlled in a way predicted by a simple thermodynamic model. We demonstrate the uniformity of the nanoisland ensembles for an area larger than 1 cm2. GaN nanowires are fabricated by a sequence of dry and wet etching steps, and these nanowires inherit the diameters and density of the Pt nanoisland ensemble used as a mask. Our study achieves advancements in size uniformity and range of obtainable diameters compared to previous works. This simple, economical, and scalable approach to the top-down fabrication of nanowires is useful for applications requiring large and uniform nanowire ensembles with controllable dimensions.

Growth mechanisms in molecular beam epitaxy for GaN-(In,Ga)N core-shell nanowires emitting in the green spectral range.

Using molecular beam epitaxy, we demonstrate the growth of (In,Ga)N shells emitting in the green spectral range around very thin (35 nm diameter) GaN core nanowires. These GaN nanowires are obtained by self-assembled growth on TiN. We present a qualitative shell growth model accounting for both the three-dimensional nature of the nanostructures as well as the directionality of the atomic fluxes. This model allows us, on the one hand, to optimise the conditions for high and homogeneous In incorporation and, on the other hand, to explain the influence of changes in the growth conditions on the sample morphology and In content. Specifically, the impact of the V/III and In/Ga flux ratios, the rotation speed and the rotation direction are investigated. Notably, with In acting as surfactant, the ternary (In,Ga)N shells are much more homogeneous in thickness along the nanowire length than their binary GaN counterparts.

Transition from elastic to plastic strain release in core-shell nanowires revealed by in-plane x-ray diffraction.

We investigate the strain evolution and relaxation process as function of increasing lattice mismatch between the GaAs core and surrounding In x Ga1-x As shell in core-shell nanowire heterostructures grown on Si(111) substrates. The dimensions of the core and shell are kept constant whereas the indium concentration inside the shell is varied. Measuring the [Formula: see text] and [Formula: see text] in-plane Bragg reflections normal to the nanowire side edges and side facets, we observe a transition from elastic to plastic strain release for a shell indium content x > 0.5. Above the onset of plastic strain relaxation, indium rich mounds and an indium poor coherent shell grow simultaneously around the GaAs core. Mound formation was observed for indium contents x = 0.5 and 0.6 by scanning electron microscopy. Considering both the measured radial reflections and the axial 111 Bragg reflection, the 3D strain variation was extracted separately for the core and the In x Ga1-x As shell.

In situx-ray analysis of misfit strain and curvature of bent polytypic GaAs-InxGa1-xAs core-shell nanowires.

Misfit strain in core-shell nanowires can be elastically released by nanowire bending in case of asymmetric shell growth around the nanowire core. In this work, we investigate the bending of GaAs nanowires during the asymmetric overgrowth by an InxGa1-xAs shell caused by avoiding substrate rotation. We observe that the nanowire bending direction depends on the nature of the substrate's oxide layer, demonstrated by Si substrates covered by native and thermal oxide layers. Further, we follow the bending evolution by time-resolvedin situx-ray diffraction measurements during the deposition of the asymmetric shell. The XRD measurements give insight into the temporal development of the strain as well as the bending evolution in the core-shell nanowire.

Beam damage of single semiconductor nanowires during X-ray nanobeam diffraction experiments.

Nanoprobe X-ray diffraction (nXRD) using focused synchrotron radiation is a powerful technique to study the structural properties of individual semiconductor nanowires. However, when performing the experiment under ambient conditions, the required high X-ray dose and prolonged exposure times can lead to radiation damage. To unveil the origin of radiation damage, a comparison is made of nXRD experiments carried out on individual semiconductor nanowires in their as-grown geometry both under ambient conditions and under He atmosphere at the microfocus station of the P08 beamline at the third-generation source PETRA III. Using an incident X-ray beam energy of 9 keV and photon flux of 1010 s-1, the axial lattice parameter and tilt of individual GaAs/In0.2Ga0.8As/GaAs core-shell nanowires were monitored by continuously recording reciprocal-space maps of the 111 Bragg reflection at a fixed spatial position over several hours. In addition, the emission properties of the (In,Ga)As quantum well, the atomic composition of the exposed nanowires and the nanowire morphology were studied by cathodoluminescence spectroscopy, energy-dispersive X-ray spectroscopy and scanning electron microscopy, respectively, both prior to and after nXRD exposure. Nanowires exposed under ambient conditions show severe optical and morphological damage, which was reduced for nanowires exposed under He atmosphere. The observed damage can be largely attributed to an oxidation process from X-ray-induced ozone reactions in air. Due to the lower heat-transfer coefficient compared with GaAs, this oxide shell limits the heat transfer through the nanowire side facets, which is considered as the main channel of heat dissipation for nanowires in the as-grown geometry.

Efficient adjustable light couplers of integrated III-V nanowire emitters on silicon waveguides based on ring resonators.

The development of integrated vertical III-V nanowire (NW) stimulated emitters in silicon photonics while achieving an efficient light coupling through vertical III-V NW lasers into horizontal optical silicon waveguides is demanding. This is mainly due to the directionality and contradiction of the simultaneously satisfied low threshold stimulated emission conditions of the vertical NWs and efficient light coupling from the NW emitters into the horizontal silicon waveguide. However, we propose a new, to the best of our knowledge, design by taking advantage of resonating features of ring structures and theoretically demonstrate that an interfacial ring resonator between GaAs NW emitters and the silicon waveguide achieves a coupling efficiency up to about 70% at a given wavelength. We also show that the interfacial resonator enables us to adjust the coupling efficiency from about 10% to over 70%. The adjustable coupling efficiency might also be a solution to compromise between the low threshold stimulated emission of NWs and efficient light coupling for realizing efficient silicon couplers based on integrated III-V NW lasers in silicon photonics. Besides the simple fabrication process compared to counterparts, we believe that the novel structure is promising for future optical on-chip data communication in silicon photonics, and the results are expandable to varying wavelengths and materials.

Corrigendum: Optical properties of GaN nanowires grown on chemical vapor deposited-graphene (2019 Nanotechnology 30 214005).

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Impact of the Shadowing Effect on the Crystal Structure of Patterned Self-Catalyzed GaAs Nanowires.

The growth of regular arrays of uniform III-V semiconductor nanowires is a crucial step on the route toward their application-relevant large-scale integration onto the Si platform. To this end, not only does optimal vertical yield, length, and diameter uniformity have to be engineered, but also, control over the nanowire crystal structure has to be achieved. Depending on the particular application, nanowire arrays with varying area density are required for optimal device efficiency. However, the nanowire area density substantially influences the nanowire growth and presents an additional challenge for nanowire device engineering. We report on the simultaneous in situ X-ray investigation of regular GaAs nanowire arrays with different area density during self-catalyzed vapor-liquid-solid growth on Si by molecular-beam epitaxy. Our results give novel insight into selective-area growth and demonstrate that shadowing of the Ga flux, occurring in dense nanowire arrays, has a crucial impact on the evolution of nanowire crystal structure. We observe that the onset of Ga flux shadowing, dependent on array pitch and nanowire length, is accompanied by an increase of the wurtzite formation rate. Our results moreover reveal the paramount role of the secondary reflected Ga flux for VLS NW growth (specifically, that flux that is reflected directly into the liquid Ga droplet).

Correlated Nanoscale Analysis of the Emission from Wurtzite versus Zincblende (In,Ga)As/GaAs Nanowire Core-Shell Quantum Wells.

While the properties of wurtzite GaAs have been extensively studied during the past decade, little is known about the influence of the crystal polytype on ternary (In,Ga)As quantum well structures. We address this question with a unique combination of correlated, spatially resolved measurement techniques on core-shell nanowires that contain extended segments of both the zincblende and wurtzite polytypes. Cathodoluminescence hyperspectral imaging reveals a blue-shift of the quantum well emission energy by 75 ± 15 meV in the wurtzite polytype segment. Nanoprobe X-ray diffraction and atom probe tomography enable k·p calculations for the specific sample geometry to reveal two comparable contributions to this shift. First, there is a 30% drop in In mole fraction going from the zincblende to the wurtzite segment. Second, the quantum well is under compressive strain, which has a much stronger impact on the hole ground state in the wurtzite than in the zincblende segment. Our results highlight the role of the crystal structure in tuning the emission of (In,Ga)As quantum wells and pave the way to exploit the possibilities of three-dimensional band gap engineering in core-shell nanowire heterostructures. At the same time, we have demonstrated an advanced characterization toolkit for the investigation of semiconductor nanostructures.

Axial GaAs/Ga(As, Bi) nanowire heterostructures.

Bi-containing III-V semiconductors constitute an exciting class of metastable compounds with wide-ranging potential optoelectronic and electronic applications. However, the growth of III-V-Bi alloys requires group-III-rich growth conditions, which pose severe challenges for planar growth. In this work, we exploit the naturally-Ga-rich environment present inside the metallic droplet of a self-catalyzed GaAs nanowire (NW) to synthesize metastable GaAs/GaAs1-x Bi x axial NW heterostructures with high Bi contents. The axial GaAs1-x Bi x segments are realized with molecular beam epitaxy by first enriching only the vapor-liquid-solid (VLS) Ga droplets with Bi, followed by exposing the resulting Ga-Bi droplets to As2 at temperatures ranging from 270 °C to 380 °C to precipitate GaAs1-x Bi x only under the NW droplets. Microstructural and elemental characterization reveals the presence of single crystal zincblende GaAs1-x Bi x axial NW segments with Bi contents up to (10 ± 2)%. This work illustrates how the unique local growth environment present during the VLS NW growth can be exploited to synthesize heterostructures with metastable compounds.

Work function of GaAs(hkl) and its modification using PEI: mechanisms and substrate dependence.

Spin-coating of poly(ethylenimine) (PEI) has been used to reduce the work function of GaAs (001), (110), (111)A and (111)B. The magnitude of the reduction immediately after coating varies significantly from 0.51 eV to 0.69 eV and depends on the surface crystal face, on the GaAs bulk doping and on the atomic termination of the GaAs. For all samples, the work function reduction shrinks in ambient air over the first 20 hours after spin coating, but reductions around 0.2-0.3 eV persist after 1 year of storage in air. Core-level photoemission of thin film PEI degradation in air is consistent with a two-stage reaction with CO2 and H2O previously proposed in carbon capture studies. The total surface dipole from PEI coating is consistent with a combination of internal neutral amine dipole and an interface dipole whose magnitude depends on the surface termination. The contact potential difference measured by Kelvin probe force microscopy on a cleaved GaAs heterostructure is smaller on p-doped regions. This can be explained by surface doping due to the PEI, which increases the band bending on p-doped GaAs where Fermi level pinning is weak. Both surface doping and surface dipole should be accounted for when considering the effect of PEI coated on a semiconductor surface.

Nanowires Bending over Backward from Strain Partitioning in Asymmetric Core-Shell Heterostructures.

The flexibility and quasi-one-dimensional nature of nanowires offer wide-ranging possibilities for novel heterostructure design and strain engineering. In this work, we realize arrays of extremely and controllably bent nanowires comprising lattice-mismatched and highly asymmetric core-shell heterostructures. Strain sharing across the nanowire heterostructures is sufficient to bend vertical nanowires over backward to contact either neighboring nanowires or the substrate itself, presenting new possibilities for designing nanowire networks and interconnects. Photoluminescence spectroscopy on bent-nanowire heterostructures reveals that spatially varying strain fields induce charge carrier drift toward the tensile-strained outside of the nanowires, and that the polarization response of absorbed and emitted light is controlled by the bending direction. This unconventional strain field is employed for light emission by placing an active region of quantum dots at the outer side of a bent nanowire to exploit the carrier drift and tensile strain. These results demonstrate how bending in nanoheterostructures opens up new degrees of freedom for strain and device engineering.

p-Type Doping of GaN Nanowires Characterized by Photoelectrochemical Measurements.

GaN nanowires (NWs) doped with Mg as a p-type impurity were grown on Si(111) substrates by plasma-assisted molecular beam epitaxy. In a systematic series of experiments, the amount of Mg supplied during NW growth was varied. The incorporation of Mg into the NWs was confirmed by the observation of donor-acceptor pairs and acceptor-bound excitons in low-temperature photoluminescence spectroscopy. Quantitative information about the Mg concentrations was deduced from Raman scattering by local vibrational modes related to Mg. In order to study the type and density of charge carriers present in the NWs, we employed two photoelectrochemical techniques, open-circuit potential and Mott-Schottky measurements. Both methods showed the expected transition from n-type to p-type conductivity with increasing Mg doping level, and the latter characterization technique allowed us to quantify the charge carrier concentration. Beyond the quantitative information obtained for Mg doping of GaN NWs, our systematic and comprehensive investigation demonstrates the benefit of photoelectrochemical methods for the analysis of doping in semiconductor NWs in general.

Anomalous Strain Relaxation in Core-Shell Nanowire Heterostructures via Simultaneous Coherent and Incoherent Growth.

Nanoscale substrates such as nanowires allow heterostructure design to venture well beyond the narrow lattice mismatch range restricting planar heterostructures, owing to misfit strain relaxing at the free surfaces and partitioning throughout the entire nanostructure. In this work, we uncover a novel strain relaxation process in GaAs/InxGa1-xAs core-shell nanowires that is a direct result of the nanofaceted nature of these nanostructures. Above a critical lattice mismatch, plastically relaxed mounds form at the edges of the nanowire sidewall facets. The relaxed mounds and a coherent shell grow simultaneously from the beginning of the deposition with higher lattice mismatches increasingly favoring incoherent mound growth. This is in stark contrast to Stranski-Krastanov growth, where above a critical thickness coherent layer growth no longer occurs. This study highlights how understanding strain relaxation in lattice mismatched nanofaceted heterostructures is essential for designing devices based on these nanostructures.

Self-Assembly of InAs Nanostructures on the Sidewalls of GaAs Nanowires Directed by a Bi Surfactant.

Surface energies play a dominant role in the self-assembly of three-dimensional (3D) nanostructures. In this Letter, we show that using surfactants to modify surface energies can provide a means to externally control nanostructure self-assembly, enabling the synthesis of novel hierarchical nanostructures. We explore Bi as a surfactant in the growth of InAs on the {11̅0} sidewall facets of GaAs nanowires. The presence of surface Bi induces the formation of InAs 3D islands by a process resembling the Stranski-Krastanov mechanism, which does not occur in the absence of Bi on these surfaces. The InAs 3D islands nucleate at the corners of the {11̅0} facets above a critical shell thickness and then elongate along ⟨110⟩ directions in the plane of the nanowire sidewalls. Exploiting this growth mechanism, we realize a series of novel hierarchical nanostructures, ranging from InAs quantum dots on single {11̅0} nanowire facets to zigzag-shaped nanorings completely encircling nanowire cores. Photoluminescence spectroscopy and cathodoluminescence spectral line scans reveal that small surfactant-induced InAs 3D islands behave as optically active quantum dots. This work illustrates how surfactants can provide an unprecedented level of external control over nanostructure self-assembly.

Polarity-Induced Selective Area Epitaxy of GaN Nanowires.

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.

Molecular Beam Epitaxy of GaN Nanowires on Epitaxial Graphene.

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.

Quantum Dot Self-Assembly Driven by a Surfactant-Induced Morphological Instability.

In strained heteroepitaxy, two-dimensional layers can exhibit a critical thickness at which three-dimensional islands self-assemble, relieving misfit strain at the cost of an increased surface area. Here we show that such a morphological phase transition can be induced on demand using surfactants. We explore Bi as a surfactant in the growth of InAs on GaAs(110), and find that the presence of surface Bi induces Stranski-Krastanov growth of 3D islands, while growth without Bi always favors 2D layer formation. Exposing a static two monolayer thick InAs layer to Bi rapidly transforms the layer into 3D islands. Density functional theory calculations reveal that Bi as well as Sb reduce the energetic cost of 3D island formation by modifying surface energies. These 3D nanostructures behave as optically active quantum dots. This work illustrates how surfactants can enable quantum dot self-assembly where it otherwise would not occur.

Efficient methodology to correlate structural with optical properties of GaAs nanowires based on scanning electron microscopy.

Twin boundaries and boundaries between zincblende (ZB) and wurtzite (WZ) segments of GaAs-related nanowires (NWs) form intrinsic heterointerfaces with essential consequences for the application of such nanomaterials in optoelectronic devices. We show that for GaAs and GaAs/(Al, Ga)As core/shell NWs, crystal twinning along the NW axis can be imaged with a spatial resolution of 10 nm using secondary electrons in a scanning electron microscope (SEM). Changes of the crystal structure from the ZB to the WZ phase have been investigated by electron backscatter diffraction. In addition to these methods, we employ spectrally and spatially resolved cathodoluminescence measurements in the same SEM to study the correlation between the structural and optical properties in single NWs. Two GaAs/AlAs/GaAs core/shell/shell NWs differing significantly in the crystal structure along their axis have been investigated combining these three techniques in order to demonstrate the strength of the employed methodology. Our experiments show that based on commonly available SEM methods, an overview of the structural properties along an entire NW and their impact on the spectral and spatial luminescence distribution can be efficiently obtained providing a quick feedback for the optimization of growth conditions.