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.

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.

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.

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.

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.

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.

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.

Broad Band Light Absorption and High Photocurrent of (In,Ga)N Nanowire Photoanodes Resulting from a Radial Stark Effect.

The photoelectrochemical properties of (In,Ga)N nanowire photoanodes are investigated using H2O2 as a hole scavenger to prevent photocorrosion. Under simulated solar illumination, In0.16Ga0.84N nanowires grown by plasma-assisted molecular beam epitaxy show a high photocurrent of 2.7 mA/cm2 at 1.2 V vs reversible hydrogen electrode. This value is almost the theoretical maximum expected from the corresponding band gap (2.8 eV) for homogeneous bulk material without taking into account surface effects. These nanowires exhibit a higher incident photon-to-current conversion efficiency over a broader wavelength range and a higher photocurrent than a compact layer with higher In content of 28%. These results are explained by the combination of built-in electric fields at the nanowire sidewall surfaces and compositional fluctuations in (In,Ga)N, which gives rise to a radial Stark effect. This effect enables spatially indirect transitions at energies much lower than the band gap. The resulting broad band light absorption leads to high photocurrents. This benefit of the radial Stark effect in (In,Ga)N nanowires for solar harvesting applications opens up the perspective to break the theoretical limit for photocurrents.

Radial Stark Effect in (In,Ga)N Nanowires.

We study the luminescence of unintentionally doped and Si-doped InxGa1-xN nanowires with a low In content (x < 0.2) grown by molecular beam epitaxy on Si substrates. The emission band observed at 300 K from the unintentionally doped samples is centered at much lower energies (800 meV) than expected from the In content measured by X-ray diffractometry and energy dispersive X-ray spectroscopy. This discrepancy arises from the pinning of the Fermi level at the sidewalls of the nanowires, which gives rise to strong radial built-in electric fields. The combination of the built-in electric fields with the compositional fluctuations inherent to (In,Ga)N alloys induces a competition between spatially direct and indirect recombination channels. At elevated temperatures, electrons at the core of the nanowire recombine with holes close to the surface, and the emission from unintentionally doped nanowires exhibits a Stark shift of several hundreds of meV. The competition between spatially direct and indirect transitions is analyzed as a function of temperature for samples with various Si concentrations. We propose that the radial Stark effect is responsible for the broadband absorption of (In,Ga)N nanowires across the entire visible range, which makes these nanostructures a promising platform for solar energy applications.

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.

Three-dimensional magneto-photoluminescence as a probe of the electronic properties of crystal-phase quantum disks in GaAs nanowires.

Crystal-phase engineering has emerged as a novel method of bandgap engineering, made feasible by the high surface-to-volume ratio of nanowires. There remains intense debate about the exact characteristics of the band structure of the novel crystal phases, such as wurtzite GaAs, obtained by this approach. We attack this problem via a low-temperature angle-dependent magneto-photoluminescence study of wurtzite/zinc-blende quantum disks in single GaAs nanowires. The exciton diamagnetic coefficient is proportional to the electron-hole correlation length, enabling a determination of the spatial extent of the exciton wave function in the plane and along the confinement axis of the crystal-phase quantum disks. Depending on the disk nature, the diamagnetic coefficient measured in Faraday geometry ranges between 25 and 75 µeV/T(2). For a given disk, the diamagnetic coefficient remains constant upon rotation of the magnetic field. Along with our envelope function calculation accounting for excitonic effects, we demonstrate that the electron effective mass in wurtzite GaAs quantum disks is heavy, mostly isotropic and results from mixing of the two lower-energy conduction bands with Γ7 and Γ8 symmetries. Finally, we discuss the implications of the results of the angle dependent magneto-luminescence for the likely symmetry of the exciton states. This work provides important insight in the band structure of wurtzite GaAs for future nanowire-based polytypic bandgap engineering.

Biexciton emission and crystalline quality of ZnO nano-objects.

The design of cost-effective standards for the quality of nano-objects is currently a key issue toward their massive use for optoelectronic applications. The observation by photoluminescence of narrow excitonic and biexcitonic emission lines in semiconductor nanowires is usually accepted as evidence for high structural quality. Here, we perform time-resolved cathodoluminescence experiments on isolated ZnO nanobelts grown by chemical vapor deposition. We observe narrow emission lines at low temperature, together with a clear biexciton line. Still, drastic alterations in both the CL intensity and lifetime are observed locally along the nano-object. We attribute these to non-radiative recombinations at edge dislocations, closing basal plane stacking faults, inhomogeneously distributed along the NB length. This leads us to the conclusion that the observation of narrow excitonic and biexcitonic emission lines is far from sufficient to grade the quality of a nano-object.