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.

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.

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.

Drastic Effect of Sequential Deposition Resulting from Flux Directionality on the Luminescence Efficiency of Nanowire Shells.

Core-shell nanowire heterostructures form the basis for many innovative devices. When compound nanowire shells are grown by directional deposition techniques, the azimuthal position of the sources for the different constituents in the growth reactor, substrate rotation, and nanowire self-shadowing inevitably lead to sequential deposition. Here, we uncover for In0.15Ga0.85As/GaAs shell quantum wells grown by molecular beam epitaxy a drastic impact of this sequentiality on the luminescence efficiency. The photoluminescence intensity of shell quantum wells grown with a flux sequence corresponding to migration enhanced epitaxy, that is, when As and the group-III metals essentially do not impinge at the same time, is more than 2 orders of magnitude higher than for shell quantum wells prepared with substantially overlapping fluxes. Transmission electron microscopy does not reveal any extended defects explaining this difference. Our analysis of photoluminescence transients shows that co-deposition has two detrimental microscopic effects. First, a higher density of electrically active point defects leads to internal electric fields reducing the electron-hole wave function overlap. Second, more point defects form that act as nonradiative recombination centers. Our study demonstrates that the source arrangement of the growth reactor, which is of mere technical relevance for planar structures, can have drastic consequences for the material properties of nanowire shells. We expect that this finding holds good also for other alloy nanowire shells.

Application of electron tomography for comprehensive determination of III-V interface properties.

We present an electron tomography method for the comprehensive characterization of buried III-V semiconductor interfaces that is based on chemical-sensitive high-angle annular dark-field scanning transmission electron microscopy. For this purpose, an (Al,Ga)As/GaAs multi-layer system grown by molecular beam epitaxy is used as a case study. Isoconcentration surfaces are exploited to obtain topographic height maps of 120 nm × 120 nm area, revealing the interface morphology. By applying the height-height correlation function, we are able to determine important interface properties like root mean square roughness and lateral correlation length of various interfaces of the (Al,Ga)As/GaAs system characterized by different Al concentrations. Height-difference maps based on isosurfaces corresponding to 30% and 70% of the total compositional difference at the interfaces are used to create topographic maps of the interface width and to calculate an average interface width. This methodology proves differences in the properties of direct and inverted interfaces and allows the observation of interfacial anisotropies.

Engineering grain boundaries at the 2D limit for the hydrogen evolution reaction.

Atom-thin transition metal dichalcogenides (TMDs) have emerged as fascinating materials and key structures for electrocatalysis. So far, their edges, dopant heteroatoms and defects have been intensively explored as active sites for the hydrogen evolution reaction (HER) to split water. However, grain boundaries (GBs), a key type of defects in TMDs, have been overlooked due to their low density and large structural variations. Here, we demonstrate the synthesis of wafer-size atom-thin TMD films with an ultra-high-density of GBs, up to ~1012 cm-2. We propose a climb and drive 0D/2D interaction to explain the underlying growth mechanism. The electrocatalytic activity of the nanograin film is comprehensively examined by micro-electrochemical measurements, showing an excellent hydrogen-evolution performance (onset potential: -25 mV and Tafel slope: 54 mV dec-1), thus indicating an intrinsically high activation of the TMD GBs.

Electron Tomography of Pencil-Shaped GaN/(In,Ga)N Core-Shell Nanowires.

The three-dimensional structure of GaN/(In,Ga)N core-shell nanowires with multi-faceted pencil-shaped apex is analyzed by electron tomography using high-angle annular dark-field mode in a scanning transmission electron microscope. Selective area growth on GaN-on-sapphire templates using a patterned mask is performed by molecular beam epitaxy to obtain ordered arrays of uniform nanowires. Our results of the tomographic reconstruction allow the detailed determination of the complex morphology of the inner (In,Ga)N multi-faceted shell structure and its deviation from the perfect hexagonal symmetry. The tomogram unambiguously identifies a dot-in-a-wire configuration at the nanowire apex including the exact shape and size, as well as the spatial distribution of its chemical composition.

Excitonic Aharonov-Bohm Oscillations in Core-Shell Nanowires.

Phase coherence in nanostructures is at the heart of a wide range of quantum effects such as Josephson oscillations between exciton-polariton condensates in microcavities, conductance quantization in 1D ballistic transport, or the optical (excitonic) Aharonov-Bohm effect in semiconductor quantum rings. These effects only occur in structures of the highest perfection. The 2D semiconductor heterostructures required for the observation of Aharonov-Bohm oscillations have proved to be particularly demanding, since interface roughness or alloy fluctuations cause a loss of the spatial phase coherence of excitons, and ultimately induce exciton localization. Experimental work in this field has so far relied on either self-assembled ring structures with very limited control of shape and dimension or on lithographically defined nanorings that suffer from the detrimental effects of free surfaces. Here, it is demonstrated that nanowires are an ideal platform for studies of the Aharonov-Bohm effect of neutral and charged excitons, as they facilitate the controlled fabrication of nearly ideal quantum rings by combining all-binary radial heterostructures with axial crystal-phase quantum structures. Thanks to the atomically flat interfaces and the absence of alloy disorder, excitonic phase coherence is preserved even in rings with circumferences as large as 200 nm.

Toward heterostructured transition metal hybrids with highly promoted electrochemical hydrogen evolution.

It is essential to precisely develop low-cost and sustainable electrocatalysts for the hydrogen evolution reaction. Herein, we explore a robust and controllable hydrothermal approach to synthesize defect-rich MoS2 nanoflakes on exfoliated MoS2 and WS2. Such well-designed hetero-structural hybrids of MoS2/exfoliated MoS2 and MoS2/exfoliated WS2 exhibit dramatically promoted electrochemical activity and high stability. The as-grown MoS2 nanoflakes hybridized on exfoliated MoS2 and WS2 generate abundant active edge sites (rich in basal defects) and unsaturated sulfur atoms, resulting in highly enhanced electrocatalytic performance. This is expected to pave the way towards a significant improvement in transition metal dichalcogenide heterostructures as electrocatalysts.

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.

Annealing induced atomic rearrangements on (Ga,In) (N,As) probed by hard X-ray photoelectron spectroscopy and X-ray absorption fine structure.

We study the effects of annealing on (Ga0.64,In0.36) (N0.045,As0.955) using hard X-ray photoelectron spectroscopy and X-ray absorption fine structure measurements. We observed surface oxidation and termination of the N-As bond defects caused by the annealing process. Specifically, we observed a characteristic chemical shift towards lower binding energies in the photoelectron spectra related to In. This phenomenon appears to be caused by the atomic arrangement, which produces increased In-N bond configurations within the matrix, as indicated by the X-ray absorption fine structure measurements. The reduction in the binding energies of group-III In, which occurs concomitantly with the atomic rearrangements of the matrix, causes the differences in the electronic properties of the system before and after annealing.

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.

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.

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.

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.

Liquid-solid phase transition of Ge-Sb-Te alloy observed by in-situ transmission electron microscopy.

Melting and crystallization dynamics of the multi-component Ge-Sb-Te alloy have been investigated by in-situ transmission electron microscopy (TEM). Starting point of the phase transition study is an ordered hexagonal Ge1Sb2Te4 thin film on Si(111) where the crystal structure and the chemical composition are verified by scanning TEM and electron energy-loss spectroscopy, respectively. The in-situ observation of the liquid phase at 600°C including the liquid-solid and liquid-vacuum interfaces and their movements was made possible due to an encapsulation of the TEM sample. The solid-liquid interface during melting displays a broad and diffuse transition zone characterized by a vacancy induced disordered state. Although the velocities of interface movements are measured to be in the nanometer per second scale, both, for crystallization and solidification, the underlying dynamic processes are considerably different. Melting reveals linear dependence on time, whereas crystallization exhibits a non-linear time-dependency featuring a superimposed start-stop motion. Our results may provide valuable insight into the atomic mechanisms at interfaces during the liquid-solid phase transition of Ge-Sb-Te alloys.

Metal-Semiconductor Phase-Transition in WSe2(1-x) Te2x Monolayer.

A metal-semiconductor phase transition in a ternary transition metal dichalcogenide (TMD) monolayer is achieved by alloying Te into WSe2 (WSe2(1-x) Te2x , where x = 0%-100%). The optical bandgaps of the WSe2(1-x) Te2x monolayer can be tuned from 1.67 to 1.44 eV (2H semiconductor) and drops to 0 eV (1Td metal), which opens up an exciting opportunity in functional electronic/optoelectronic devices.

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.

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.

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.