Achieving quantum confinement by bottom-up growth of nanowires has so far been limited to the ability of obtaining stable metal droplets of radii around 10 nm or less. This is within reach for gold-assisted growth. Because of the necessity to maintain the group III droplets during growth, direct synthesis of quantum sized structures becomes much more challenging for self-assisted III−V nanowires. In this work, we elucidate and solve the challenges that involve the synthesis of galliumassisted quantum-sized GaAs nanowires. We demonstrate the existence of two stable contact angles for the gallium droplet on top of GaAs nanowires. Contact angle around 130°fosters a continuous increase in the nanowire radius, while 90°allows for the stable growth of ultrathin tops. The experimental results are fully consistent with our model that explains the observed morphological evolution under the two different scenarios. We provide a generalized theory of self-assisted III−V nanowires that describes simultaneously the droplet shape relaxation and the NW radius evolution. Bistability of the contact angle described here should be the general phenomenon that pertains for any vapor−liquid−solid nanowires and significantly refines our picture of how nanowires grow. Overall, our results suggest a new path for obtaining ultrathin one-dimensional III−V nanostructures for studying lateral confinement of carriers. KEYWORDS: III−V semiconductors on silicon, nanowires, nanoneedles, regular arrays, self-assisted growth, droplet size engineering, crystal structure, growth modeling F undamental physical properties and applications of semiconductor nanowires (NWs) may benefit from quantum confinement due to size-dependent modulation of the density of states as well as modification of the photon energy for the allowed optical transitions.1 In GaAs, quantum confinement occurs for a size below 25 nm.2,3 In addition to quantum confinement, the optical properties can be engineered by modifying the NW shape. For example, progressively tapered nanowires have exhibited adiabatic outcoupling in the emission of quantum dots, thereby enhancing their brightness. 4 A similar design may improve the light extraction or absorption in different optoelectronic devices including light emitting diodes, solar cells, and optical biosensors.5−11 Quantum confinement in the core of radial NW heterostructures allows for the fabrication of high quality NW-based quantum dots, which are a perfect platform for delicate quantum transport experiments. 12,13 It is admittedly challenging to obtain very thin (quantumconfined) III−V NWs directly by the vapor−liquid−solid (VLS) growth technique. There are several reasons for that (see ref 14 for a review), including the Gibbs−Thomson effect of elevation of chemical potential due to the curvature of the droplet surface and difficulties in obtaining very small droplets on the substrate surface. Thin tips of VLS GaAs NWs with a stable radius down to 5 nm have previously been grown by hydride vapor phase epitaxy 15,16 (a te...

GaAs/Al-GaAs core-shell nanowires fabricated by molecular beam epitaxy contain quantum confining structures susceptible of producing narrow photoluminescence (PL) and single photons. The nanoscale chemical mapping of these structures is analyzed in 3D by atom probe tomography (APT). The study allows us to confirm that Al atoms tend to segregate within the AlGaAs shells towards the vertices of the hexagons defining the nanowire cross section. We also find strong alloy fluctuations remaining AlGaAs shell, leading occasionally to the formation of quantum dots (QDs). The PL emission energies predicted in the framework of a 3D effective mass model for a QD analyzed by APT and the PL spectra measured on other nanowires from the same growth batch are consistent within the experimental uncertainties. V C 2014 AIP Publishing LLC.[http://dx.doi.org/10.1063/1.4904952] Epitaxial semiconductor quantum dots (QDs) have been extensively studied over the last three decades because of their peculiar optical properties such as narrow luminescence and single photon emission. The structure and chemical composition of QDs has traditionally been assessed by scanning tunneling microscopy (STM) or transmission electron microscopy (TEM) related techniques. 1 In the last decade, laser-assisted atom probe tomography (LA-APT) 2 has emerged as a tool for the determination of the morphology and of the chemical composition of nanoscale semiconductor heterostructures with sub-nanometer resolution in 3D. 3,4 In the past few years, several APT-based studies addressed a limited number of QD structures. 4-10 Quantum dots can be inserted in semiconductor nanowires either deterministically, with specific shape and composition, 11-14 or as self-assembled structures. [15][16][17][18] Nanowires, furthermore, represent a model system for atom probe analysis, 19-24 as they closely approximate the shape of a field-emission tip. Nevertheless, and despite the interest of nanowire-based QDs for quantum information [25][26][27][28][29] and for their integration in nanoscale optoelectronic devices, [30][31][32][33] no studies of nanowire QDs by APT have been reported yet.Core-shell GaAs/AlGaAs nanowires grown by molecular beam epitaxy (MBE) have been shown to exhibit narrow luminescence and single photon emission, ascribed to QDs forming occasionally at the external corners of the AlGaAs shells. 27 Isolated emissions centered around 670 nm ($1.85 eV) could be found by cathodoluminescence (CL) spectroscopy, with a typical mean frequency along the axis of the order of one spot per micron. 27 Previous studies of these structures performed by highresolution scanning transmission electron microscopy (HR-STEM), electron energy loss spectroscopy (EELS), and energy-dispersive X-ray spectroscopy (EDX) indicated that QDs may form at the outer corner of the hexagon in the AlGaAs shell, at the termination of an Al-segregation region. 27,34 However, it was not possible to fully characterize the shape of the dots nor ascertain whether other mechanisms of QD formation may occ...

Compound semiconductors exhibit an intrinsic polarity, as a consequence of the ionicity of their bonds. Nanowires grow mostly along the (111) direction for energetic reasons. Arsenide and phosphide nanowires grow along (111)B, implying a group V termination of the (111) bilayers. Polarity engineering provides an additional pathway to modulate the structural and optical properties of semiconductor nanowires. In this work, we demonstrate for the first time the growth of Ga-assisted GaAs nanowires with (111)A-polarity, with a yield of up to ∼50%. This goal is achieved by employing highly Ga-rich conditions which enable proper engineering of the energies of A and B-polar surfaces. We also show that A-polarity growth suppresses the stacking disorder along the growth axis. This results in improved optical properties, including the formation of AlGaAs quantum dots with two orders or magnitude higher brightness. Overall, this work provides new grounds for the engineering of nanowire growth directions, crystal quality and optical functionality.

We demonstrate the selective area growth of GaN−(Al,Ga)N core−shell nanowire heterostructures directly on Si(111). Photoluminescence spectroscopy on as-grown nanowires reveals a strong blueshift of the GaN band gap from 3.40 to 3.64 eV at room temperature. Raman measurements relate this shift to compressive strain within the GaN core. On the nanoscale, cathodoluminescence spectroscopy and scanning transmission electron microscopy prove the homogeneity of strain-related luminescence along the nanowire axis and the absence of significant fluctuations within the shell, respectively. A comparison of the experimental findings with numerical simulations indicates the absence of a significant defect-related strain relaxation for all investigated structures, with a maximum compressive strain of −3.4% for a shell thickness of 50 nm. The accurate control of the nanowire dimensions, namely, core diameter, shell thickness, and nanowire period, via selective area growth allows a specific manipulation of the resulting strain within individual nanowires on the same sample. This, in turn, enables a spatially resolved adjustment of the GaN band gap with an energy range of 240 meV in a one-step growth process.

III–V integration on Si(100) is a challenge: controlled vertical vapor liquid solid nanowire growth on this platform has not been reported so far. Here we demonstrate an atypical GaAs vertical nanostructure on Si(100), coined nanospade, obtained by a nonconventional droplet catalyst pinning. The Ga droplet is positioned at the tip of an ultrathin Si pillar with a radial oxide envelope. The pinning at the Si/oxide interface allows the engineering of the contact angle beyond the Young–Dupré equation and the growth of vertical nanospades. Nanospades exhibit a virtually defect-free bicrystalline nature. Our growth model explains how a pentagonal twinning event at the initial stages of growth provokes the formation of the nanospade. The optical properties of the nanospades are consistent with the high crystal purity, making these structures viable for use in integration of optoelectronics on the Si(100) platform.

Quantum dots (QDs) embedded in nanowires represent one of the most promising technologies for applications in quantum photonics. Self-assembled bottom-up fabrication is attractive to overcome the technological challenges involved in a top-down approach, but it needs post-growth investigations in order to understand the self-organization process. We investigate the QD formation by selfsegregation in Al x Ga 1Àx As shells as a function of thickness and cross-section morphology. By analysing light emission from several hundreds of emitters, we find that there is a certain thickness threshold for the observation of the QDs. The threshold becomes smaller if a thin AlAs layer is pre-deposited between the GaAs nanowire core and the Al x Ga 1Àx As shell. Our results evidence the development of the quantum emitters during the shell growth and provide more guidance for their use in quantum photonics. V C 2015 AIP Publishing LLC. [http://dx

Two-dimensional semiconductors, in particular transition metal dichalcogenides and related heterostructures, have gained increasing interest as they constitute potential new building blocks for the next generation of electronic and optoelectronic applications. In this work, we develop a novel nondestructive and noncontact technique for mapping the absorption properties of 2D materials, by taking advantage of the underlying substrate cathodoluminescence emission. We map the quantitative absorption of MoS2 and MoSe2 monolayers, obtained on sapphire and oxidized silicon, with nanoscale resolution. We extend our technique to the characterization of the absorption properties of MoS2/MoSe2 van der Waals heterostructures. We demonstrate that interlayer excitonic phenomena enhance the absorption in the UV range. Our technique also highlights the presence of defects such as grain boundaries and ad-layers. We provide measurements on the absorption of grain boundaries in monolayer MoS2 at different merging angles. We observe a higher absorption yield of randomly oriented monolayers with respect to 60° rotated monolayers. This work opens up a new possibility for characterizing the functional properties two-dimensional semiconductors at the nanoscale.

The nature of the liquid–solid interface determines the characteristics of a variety of physical phenomena, including catalysis, electrochemistry, lubrication, and crystal growth. Most of the established models for crystal growth are based on macroscopic thermodynamics, neglecting the atomistic nature of the liquid–solid interface. Here, experimental observations and molecular dynamics simulations are employed to identify the 3D nature of an atomic‐scale ordering of liquid Ga in contact with solid GaAs in a nanowire growth configuration. An interplay between the liquid ordering and the formation of a new bilayer is revealed, which, contrary to the established theories, suggests that the preference for a certain polarity and polytypism is influenced by the atomic structure of the interface. The conclusions of this work open new avenues for the understanding of crystal growth, as well as other processes and systems involving a liquid–solid interface.