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.

Large-Area Synthesis of Ferromagnetic Fe5- x GeTe2 /Graphene van der Waals Heterostructures with Curie Temperature above Room Temperature.

Van der Waals (vdW) heterostructures combining layered ferromagnets and other 2D crystals are promising building blocks for the realization of ultracompact devices with integrated magnetic, electronic, and optical functionalities. Their implementation in various technologies depends strongly on the development of a bottom-up scalable synthesis approach allowing for realizing highly uniform heterostructures with well-defined interfaces between different 2D-layered materials. It is also required that each material component of the heterostructure remains functional, which ideally includes ferromagnetic order above room temperature for 2D ferromagnets. Here, it is demonstrated that the large-area growth of Fe5- x GeTe2 /graphene heterostructures is achieved by vdW epitaxy of Fe5- x GeTe2 on epitaxial graphene. Structural characterization confirms the realization of a continuous vdW heterostructure film with a sharp interface between Fe5- x GeTe2 and graphene. Magnetic and transport studies reveal that the ferromagnetic order persists well above 300 K with a perpendicular magnetic anisotropy. In addition, epitaxial graphene on SiC(0001) continues to exhibit a high electronic quality. These results represent an important advance beyond nonscalable flake exfoliation and stacking methods, thus marking a crucial step toward the implementation of ferromagnetic 2D materials in practical applications.

Crystal-Phase Quantum Wires: One-Dimensional Heterostructures with Atomically Flat Interfaces.

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

Growth mode evolution during (100)-oriented ß-Ga2O3 homoepitaxy.

This work focuses on homoepitaxial growth of ß-Ga2O3 on (100)-oriented substrates during molecular beam epitaxy. It provides a comprehensive study on the growth mode by combining in situ with ex situ tools. In situ reflection high-energy electron diffraction (RHEED) indicates 2D layer-by-layer mode accompanied by (1 × 1) surface reconstruction. The homoepitaxial layers are grown pseudomorphic with the substrate without in-plane strain as probed by in-plane azimuthal RHEED and out-of-plane synchrotron-based high resolution x-ray diffraction. In contrast to the substrate, stacking faults and twin domains are present in the layer.

Strain Driven Shape Evolution of Stacked (In,Ga)N Quantum Disks Embedded in GaN Nanowires.

The fabrication of nanowires with axial multiquantum wells or disks presenting a homogeneous size and shape distribution along the whole stack is still an unresolved challenge, despite being essential for narrowing their light emission bandwidth. In this work we demonstrate that the commonly observed change in the shape of the disks along the stacking direction proceeds in a systematic, predictable way. High- resolution transmission electron microscopy of stacked (In,Ga)N quantum discs embedded in GaN nanowires with diameters of ∼40 nm and lengths of ∼700 nm and finite element method calculations show that, contrary to what is normally assumed, this change is not related to the radial growth of the nanowires, which is shown to be negligible, but to the strain relaxation of the whole active region. A simple model is proposed to account for the experimental observations. The model assumes that each disk reaches an equilibrium shape that minimizes the overall energy of the system, given by the sum of the surface and strain energies of the disk itself and the barrier below. The strain state of the barrier is affected by the presence of the disk buried directly below in a way that depends on its shape. This gives rise to a cumulative process, which makes the aspect ratio of each quantum disk to be smaller compared to the disk grown just before, in qualitative agreement with the experimental observations. The obtained results imply that strain relaxation is an important factor to bear in mind for the design of multiquantum disks with controlled shape along the stacking direction in any lattice mismatched nanowire system.

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.

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.

Observation of Dielectrically Confined Excitons in Ultrathin GaN Nanowires up to Room Temperature.

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

Nanofocus x-ray diffraction and cathodoluminescence investigations into individual core-shell (In,Ga)N/GaN rod light-emitting diodes.

Employing nanofocus x-ray diffraction, we investigate the local strain field induced by a five-fold (In,Ga)N multi-quantum well embedded into a GaN micro-rod in core-shell geometry. Due to an x-ray beam width of only 150 nm in diameter, we are able to distinguish between individual m-facets and to detect a significant in-plane strain gradient along the rod height. This gradient translates to a red-shift in the emitted wavelength revealed by spatially resolved cathodoluminescence measurements. We interpret the result in terms of numerically derived in-plane strain using the finite element method and subsequent kinematic scattering simulations which show that the driving parameter for this effect is an increasing indium content towards the rod tip.

Fano-like resonances sustained by Si doped InAsSb plasmonic resonators integrated in GaSb matrix.

By using metal-free plasmonics, we report on the excitation of Fano-like resonances in the mid-infrared where the Fano asymmetric parameter, q, varies when the dielectric environment of the plasmonic resonator changes. We use silicon doped InAsSb alloy deposited by molecular beam epitaxy on GaSb substrate to realize the plasmonic resonators exclusively based on semiconductors. We first demonstrate the possibility to realize high quality samples of embedded InAsSb plasmonic resonators into GaSb host using regrowth technique. The high crystalline quality of the deposited structure is confirmed by scanning transmission electron microscopy (STEM) observation. Second, we report Fano-like resonances associated to localized surface plasmons in both cases: uncovered and covered plasmonic resonators, demonstrating a strong line shape modification. The optical properties of the embedded structures correspond to those modeled by finite-difference time-domain (FDTD) method and by a model based on Fano-like line shape. Our results show that all-semiconductor plasmonics gives the opportunity to build new plasmonic structures with embedded resonators of highly doped semiconductor in a matrix of un-doped semiconductor for mid-IR applications.

Detecting lateral composition modulation in dilute Ga(As,Bi) epilayers.

The ability to characterize a structure into the finest details in a quantitative manner is a key issue to understanding and controlling nanoscale phase separation in novel nanomaterials. In this work, we consider the detectability of lateral composition modulation (LCM), a type of nanoscale phase separation in GaAs(1-x)Bix epilayers, by x-ray diffraction (XRD). We show that the satellite peaks due to LCM are hardly detectable in reasonable time with a lab x-ray diffractometer for GaAs(1-x)Bix samples with an average x up to 25% and relative modulation up to 50%. This is in contrast to LCM reported in other III-V combinations, where the intensity of the satellite peak is relatively high and can be easily detected. Our theoretical considerations are complemented experimentally using highly brilliant synchrotron radiation. The results are in good agreement with the predictions. This work provides a guideline for the systematic characterization of LCM in zincblende III-V semiconductor epilayers and points to the critical role of quantitative characterization of nanoscale phase separation.

Coaxial multishell (In,Ga)As/GaAs nanowires for near-infrared emission on Si substrates.

Efficient infrared light emitters integrated on the mature Si technology platform could lead to on-chip optical interconnects as deemed necessary for future generations of ultrafast processors as well as to nanoanalytical functionality. Toward this goal, we demonstrate the use of GaAs-based nanowires as building blocks for the emission of light with micrometer wavelength that are monolithically integrated on Si substrates. Free-standing (In,Ga)As/GaAs coaxial multishell nanowires were grown catalyst-free on Si(111) by molecular beam epitaxy. The emission properties of single radial quantum wells were studied by cathodoluminescence spectroscopy and correlated with the growth kinetics. Controlling the surface diffusivity of In adatoms along the NW side-walls, we improved the spatial homogeneity of the chemical composition along the nanowire axis and thus obtained a narrow emission spectrum. Finally, we fabricated a light-emitting diode consisting of approximately 10(5) nanowires contacted in parallel through the Si substrate. Room-temperature electroluminescence at 985 nm was demonstrated, proving the great potential of this technology.

Formation and phase transformation of Bi-containing QD-like clusters in annealed GaAsBi.

We report the formation and phase transformation of Bi-containing clusters in GaAs(1-x)Bi(x) epilayers upon annealing. The GaAs(1-x)Bi(x) layers were grown by molecular beam epitaxy under low (220 °C) and high (315 °C) temperatures and subsequently annealed using different temperatures and annealing times. Bi-containing clusters were identified only in the annealed samples that were grown at low temperature, revealing a relatively homogeneous size distribution. Depending on the annealing temperature and duration, the clusters show different sizes ranging from 5 to 20 nm, as well as different crystallographic phase, being coherently strained zincblende GaAs(1-x)Bi(x) (zb Bi-rich Ga(As, Bi)) clusters or rhombohedral pure Bi (rh-Bi) clusters. We found that: (1) the formation of the zb Bi-rich Ga(As, Bi) clusters is driven by the intrinsic tendency of the alloy to phase separately and is mediated by the native point defects present in the low temperature grown epilayers; (2) the phase transformation from zb Bi-rich Ga(As, Bi) to rh-Bi nucleates in zincblende {111} planes and grows until total consumption of Bi in the GaAs matrix. We propose a model accounting for the formation and phase transformation of Bi-containing clusters in this system. Furthermore, our study reveals the possibility to realize self-organized zb Bi-rich Ga(As, Bi) clusters that can exhibit QD-like features.

Investigation of III-V nanowires by plan-view transmission electron microscopy: InN case study.

We discuss observations of InN nanowires (NWs) by plan-view high-resolution transmission electron microscopy (TEM). The main difficulties arise from suitable methods available for plan-view specimen preparation. We explore different approaches and find that the best results are obtained using a refined preparation method based on the conventional procedure for plan-view TEM of thin films, specifically modified for the NW morphology. The fundamental aspects of such a preparation are the initial mechanical stabilization of the NWs and the minimization of the ion-milling process after dimpling the samples until perforation. The combined analysis by plan-view and cross-sectional TEM of the NWs allows determination of the degree of strain relaxation and reveals the formation of an unintentional shell layer (2-3-nm thick) around the InN NWs. The shell layer is composed of bcc In2O3 nanocrystals with a preferred orientation with respect to the wurtzite InN: In2O3 [111] || InN [0001] and In2O3<110>||InN<1120>.

Control over the number density and diameter of GaAs nanowires on Si(111) mediated by droplet epitaxy.

We present a novel approach for the growth of GaAs nanowires (NWs) with controllable number density and diameter, which consists of the combination between droplet epitaxy (DE) and self-assisted NW growth. In our method, GaAs islands are initially formed on Si(111) by DE and, subsequently, GaAs NWs are selectively grown on their top facet, which acts as a nucleation site. By DE, we can successfully tailor the number density and diameter of the template of initial GaAs islands and the same degree of control is transferred to the final GaAs NWs. We show how, by a suitable choice of V/III flux ratio, a single NW can be accommodated on top of each GaAs base island. By transmission electron microscopy, as well as cathodo- and photoluminescence spectroscopy, we confirmed the high structural and optical quality of GaAs NWs grown by our method. We believe that this combined approach can be more generally applied to the fabrication of different homo- or heteroepitaxial NWs, nucleated on the top of predefined islands obtained by DE.

GaAs-Fe3Si core-shell nanowires: nanobar magnets.

Semiconductor-ferromagnet GaAs-Fe3Si core-shell nanowires were grown by molecular beam epitaxy and analyzed by scanning and transmission electron microscopy, X-ray diffraction, Mössbauer spectroscopy, and magnetic force microscopy. We obtained closed and smooth Fe3Si shells with a crystalline structure that show ferromagnetic properties with magnetizations along the nanowire axis (perpendicular to the substrate). Such nanobar magnets are promising candidates to enable the fabrication of new forward-looking devices in the field of spintronics and magnetic recording.

Three-Dimensional Reconstruction of Interface Roughness and Alloy Disorder in Ge/GeSi Asymmetric Coupled Quantum Wells Using Electron Tomography.

Interfaces play an essential role in the performance of ever-shrinking semiconductor devices, making comprehensive determination of their three-dimensional (3D) structural properties increasingly important. This becomes even more relevant in compositional interfaces, as is the case for Ge/GeSi heterostructures, where chemical intermixing is pronounced in addition to their morphology. We use the electron tomography method to reconstruct buried interfaces and layers of asymmetric coupled Ge/Ge0.8Si0.2 multiquantum wells, which are considered a potential building block in THz quantum cascade lasers. The three-dimensional reconstruction is based on a series of high-angle annular dark-field scanning transmission electron microscopy images. It allows chemically sensitive investigation of a relatively large interfacial area of about (80 × 80) nm2 with subnanometer resolution as well as the analysis of several interfaces within the multiquantum well stack. Representing the interfaces as iso-concentration surfaces in the tomogram and converting them to topographic height maps allows the determination of their morphological roughness as well as layer thicknesses, reflecting low variations in either case. Simulation of the reconstructed tomogram intensities using a sigmoidal function provides in-plane-resolved maps of the chemical interface widths showing a relatively large spatial variation. The more detailed analysis of the intermixed region using thin slices from the reconstruction and additional iso-concentration surfaces provides an accurate picture of the chemical disorder of the alloy at the interface. Our comprehensive three-dimensional image of Ge/Ge0.8Si0.2 interfaces reveals that in the case of morphologically very smooth interfaces─depending on the scale considered─the interface alloy disorder itself determines the overall characteristics, a result that is fundamental for highly miscible material systems.

Coherent GdN clusters in epitaxial GaN:Gd thin films determined by transmission electron microscopy.

The detection of non-uniform magnetic element distribution and phase separation has been highly challenging in dilute magnetic semiconductor alloys. Here, we present a dedicated transmission electron microscopy (TEM) investigation of epitaxial GaN:Gd thin films and unambiguously identify the occurrence of nano-scale coherent GdN clusters. The films were grown by molecular beam epitaxy with Gd concentrations varying between 10(16) and 10(19) cm(-3). The TEM results revealed the presence of nano-scale, coherently strained platelets lying parallel to the (0001) basal planes of the wurtzite GaN matrix. The platelet-shaped clusters consist of GdN as verified by chemically sensitive Z-contrast scanning TEM imaging. The cluster dimension as well as the displacement of the distorted lattice along the [0001] direction are quantitatively determined by high-resolution TEM based on geometric phase analysis. Dynamic strain contrast calculations taking the measured displacement field as an input parameter attained an excellent agreement with the experimental diffraction contrast results, which enables an estimate of average cluster size and distance. The GdN platelet clusters are of two monolayer thickness with a base diameter of about 2 nm for samples with low Gd concentrations (10(16) cm(-3)) and about 4 nm for samples with high Gd concentrations (10(19) cm(-3)). A discussion about the local stress environment establishes that the GdN platelets are incorporated in a metastable wurtzite crystal phase.

Spontaneous nucleation and growth of GaN nanowires: the fundamental role of crystal polarity.

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.