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.

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.

X-ray diffraction reveals the amount of strain and homogeneity of extremely bent single nanowires.

Core-shell nanowires (NWs) with asymmetric shells allow for strain engineering of NW properties because of the bending resulting from the lattice mismatch between core and shell material. The bending of NWs can be readily observed by electron microscopy. Using X-ray diffraction analysis with a micro- and nano-focused beam, the bending radii found by the microscopic investigations are confirmed and the strain in the NW core is analyzed. For that purpose, a kinematical diffraction theory for highly bent crystals is developed. The homogeneity of the bending and strain is studied along the growth axis of the NWs, and it is found that the lower parts, i.e. close to the substrate/wire interface, are bent less than the parts further up. Extreme bending radii down to ∼3 µm resulting in strain variation of ∼2.5% in the NW core are found.

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.

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.

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.

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.

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.

Threefold rotational symmetry in hexagonally shaped core-shell (In,Ga)As/GaAs nanowires revealed by coherent X-ray diffraction imaging.

Coherent X-ray diffraction imaging at symmetric hhh Bragg reflections was used to resolve the structure of GaAs/In0.15Ga0.85As/GaAs core-shell-shell nanowires grown on a silicon (111) substrate. Diffraction amplitudes in the vicinity of GaAs 111 and GaAs 333 reflections were used to reconstruct the lost phase information. It is demonstrated that the structure of the core-shell-shell nanowire can be identified by means of phase contrast. Interestingly, it is found that both scattered intensity in the (111) plane and the reconstructed scattering phase show an additional threefold symmetry superimposed with the shape function of the investigated hexagonal nanowires. In order to find the origin of this threefold symmetry, elasticity calculations were performed using the finite element method and subsequent kinematic diffraction simulations. These suggest that a non-hexagonal (In,Ga)As shell covering the hexagonal GaAs core might be responsible for the observation.

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.