Circumventing the ammonia-related growth suppression for obtaining regular GaN nanowires by HVPE.

Selective area growth by hydride vapor phase epitaxy of GaN nanostructures with different shapes was investigated versus the deposition conditions including temperature and ammonia flux. Growth experiments were carried out on templates of GaN on sapphire masked with SiNx. We discuss two occurrences related to axial and radial growth of GaN nanowires. A growth suppression phenomenon was observed under certain conditions, which was circumvented by applying the cyclic growth mode. A theoretical model involving inhibiting species was developed to understand the growth suppression phenomenon on the masked substrates. Various morphologies of GaN nanocrystals were obtained by controlling the competition between the growth and blocking mechanisms as a function of the temperature and vapor phase composition. The optimal growth conditions were revealed for obtaining regular arrays of ∼5µm long GaN nanowires.

In-Situ Transmission Electron Microscopy Observation of Germanium Growth on Freestanding Graphene: Unfolding Mechanism of 3D Crystal Growth During Van der Waals Epitaxy.

Breakthroughs in cutting-edge research fields such as hetero-integration of materials and the development of quantum devices are heavily bound to the control of misfit strain during heteroepitaxy. While remote epitaxy offers one of the most intriguing avenues, demonstrations of functional hybrid heterostructures are hardly possible without a deep understanding of the nucleation and growth kinetics of 3D crystals on graphene and their mutual interactions. Here, the kinetics of such processes from real-time observations of germanium (Ge) growth on freestanding single layer graphene (SLG) using in-situ transmission electron microscopy are unraveled. This powerful technique provides a unique opportunity to observe new and yet unexplored phenomena, which are not accessible to the standard ex situ characterizations. Through direct observations, remote interactions are elucidated between Ge crystals through the graphene layer in double heterostructures of Ge/graphene/Ge. Notably, the data show real-time evidence of vertical Ge atoms diffusion through the graphene layer. This phenomenon is attributed to the remote interactions of Ge atoms through the graphene lattice, due to its interatomic interaction transparency. Additionally, key mechanisms governing nucleation and initial growth in graphene were systematically determined. These findings enlighten the growth mechanism of graphene and provide a new pathway for disruptive hybrid semiconductor-graphene devices.

Investigation of the effect of the doping order in GaN nanowire p-n junctions grown by molecular-beam epitaxy.

We analyse the electrical and optical properties of single GaN nanowire p-n junctions grown by plasma-assisted molecular-beam epitaxy using magnesium and silicon as doping sources. Different junction architectures having either a n-base or a p-base structure are compared using optical and electrical analyses. Electron-beam induced current (EBIC) microscopy of the nanowires shows that in the case of a n-base p-n junction the parasitic radial growth enhanced by the magnesium (Mg) doping leads to a mixed axial-radial behaviour with strong wire-to-wire fluctuations of the junction position and shape. By reverting the doping order p-base p-n junctions with a purely axial well-defined structure and a low wire-to-wire dispersion are achieved. The good optical quality of the top n nanowire segment grown on a p-doped stem is preserved. A hole concentration in the p-doped segment exceeding 1018 cm-3 was extracted from EBIC mapping and photoluminescence analyses. This high concentration is reached without degrading the nanowire morphology.

Phase Selection in Self-catalyzed GaAs Nanowires.

Crystal phase switching between the zincblende and wurtzite structures in III-V nanowires is crucial from the fundamental viewpoint as well as for electronic and photonic applications of crystal phase heterostructures. Here, the results of in situ monitoring of self-catalyzed vapor-liquid-solid growth of GaAs nanowires by molecular beam epitaxy inside a transmission electron microscope are presented. It is demonstrated that the occurrence of the zincblende or wurtzite phase in self-catalyzed nanowires is determined by the sole parameter, the droplet contact angle, which can be finely tuned by changing the group III and V fluxes. The zincblende phase forms at small (<100°) and large (>125°) contact angles, whereas pure wurtzite phase is observed for intermediate contact angles. Wurtzite nanowires are restricted by vertical sidewalls, whereas zincblende nanowires taper or develop the truncated edge at their top. These findings are explained within a dedicated model for the surface energetics. These results give a clear route for the crystal phase control in Au-free III-V nanowires. On a more general note, in situ growth monitoring with atomic resolution and at the technological-relevant growth rates is shown to be a powerful tool for the fine-tuning of material properties at the nanoscale.

Nanoscale electrical analyses of axial-junction GaAsP nanowires for solar cell applications.

Axial p-n and p-i-n junctions in GaAs0.7P0.3 nanowires are demonstrated and analyzed using electron beam induced current microscopy. Organized self-catalyzed nanowire arrays are grown by molecular beam epitaxy on nanopatterned Si substrates. The nanowires are doped using Be and Si impurities to obtain p- and n-type conductivity, respectively. A method to determine the doping type by analyzing the induced current in the vicinity of a Schottky contact is proposed. It is demonstrated that for the applied growth conditions using Ga as a catalyst, Si doping induces an n-type conductivity contrary to the GaAs self-catalyzed nanowire case, where Si was reported to yield a p-type doping. Active axial nanowire p-n junctions having a homogeneous composition along the axis are synthesized and the carrier concentration and minority carrier diffusion lengths are measured. To the best of our knowledge, this is the first report of axial p-n junctions in self-catalyzed GaAsP nanowires.

Investigation of GaN nanowires containing AlN/GaN multiple quantum discs by EBIC and CL techniques.

In this work, nanoscale electrical and optical properties of n-GaN nanowires (NWs) containing GaN/AlN multiple quantum discs (MQDs) grown by molecular beam epitaxy are investigated by means of single wire I(V) measurements, electron beam induced current microscopy (EBIC) and cathodoluminescence (CL) analysis. A strong impact of non-intentional AlN and GaN shells on the electrical resistance of individual NWs is put in evidence. The EBIC mappings reveal the presence of two regions with internal electric fields oriented in opposite directions: one in the MQDs region and the other in the adjacent bottom GaN segment. These fields are found to co-exist under zero bias, while under an external bias either one or the other dominates the current collection. In this way EBIC maps allow us to locate the current generation within the wire under different bias conditions and to give the first direct evidence of carrier collection from AlN/GaN MQDs. The NWs have been further investigated by photoluminescence and CL analyses at low temperature. CL mappings show that the near band edge emission of GaN from the bottom part of the NW is blue-shifted due to the presence of the radial shell. In addition, it is observed that CL intensity drops in the central part of the NWs. Comparing the CL and EBIC maps, this decrease of the luminescence intensity is attributed to an efficient charge splitting effect due to the electric fields in the MQDs region and in the GaN base.

Importance of point defect reactions for the atomic-scale roughness of III-V nanowire sidewalls.

The surface morphology of III-V semiconductor nanowires (NWs) protected by an arsenic cap and subsequently evaporated in ultrahigh vacuum is investigated with scanning tunneling microscopy and scanning transmission electron microscopy. We show that the changes of the surface morphology as a function of the NW composition and the nature of the seed particles are intimately related to the formation and reaction of surface point defects. Langmuir evaporation close to the congruent evaporation temperature causes the formation of vacancies which nucleate and form vacancy islands on {110} sidewalls of self-catalyzed InAs NWs. However, for annealing temperatures much smaller than the congruent temperature, a new phenomenon occurs: group III vacancies form and are filled by excess As atoms, leading to surface AsGa antisites. The resulting Ga adatoms nucleate with excess As atoms at the NW edges, producing monoatomic-step islands on the {110} sidewalls of GaAs NWs. Finally, when gold atoms diffuse from the seed particle onto the {110} sidewalls during evaporation of the protective As cap, Langmuir evaporation does not take place, leaving the sidewalls of InAsSb NWs atomically flat.

Measuring and Modeling the Growth Dynamics of Self-Catalyzed GaP Nanowire Arrays.

The bottom-up fabrication of regular nanowire (NW) arrays on a masked substrate is technologically relevant, but the growth dynamic is rather complex due to the superposition of severe shadowing effects that vary with array pitch, NW diameter, NW height, and growth duration. By inserting GaAsP marker layers at a regular time interval during the growth of a self-catalyzed GaP NW array, we are able to retrieve precisely the time evolution of the diameter and height of a single NW. We then propose a simple numerical scheme which fully computes shadowing effects at play in infinite arrays of NWs. By confronting the simulated and experimental results, we infer that re-emission of Ga from the mask is necessary to sustain the NW growth while Ga migration on the mask must be negligible. When compared to random cosine or random uniform re-emission from the mask, the simple case of specular reflection on the mask gives the most accurate account of the Ga balance during the growth.

Atomic Step Flow on a Nanofacet.

Crystal growth often proceeds by atomic step flow. When the surface area available for growth is limited, the nucleation and progression of the steps can be affected. This issue is particularly relevant to the formation of nanocrystals. We examine the case of Au-catalyzed GaAs nanowires, which we grow in a transmission electron microscope. Our in situ observations show that atomic layers nucleate at the periphery of the interface between the nanowire and the catalyst droplet. From this starting location, the atomic step flows within a restricted area of hexagonal shape. At specific partial coverages, the monolayer configuration changes abruptly. A simple model based on the geometry of the system and its edge energies explains these observations. In particular, we observe an inversion of the step curvature which reveals that the effective energy per unit length of monolayer edge is much lower at the interface periphery than inside the catalyst droplet.

Determination of n-Type Doping Level in Single GaAs Nanowires by Cathodoluminescence.

We present an effective method of determining the doping level in n-type III-V semiconductors at the nanoscale. Low-temperature and room-temperature cathodoluminescence (CL) measurements are carried out on single Si-doped GaAs nanowires. The spectral shift to higher energy (Burstein-Moss shift) and the broadening of luminescence spectra are signatures of increased electron densities. They are compared to the CL spectra of calibrated Si-doped GaAs layers, whose doping levels are determined by Hall measurements. We apply the generalized Planck's law to fit the whole spectra, taking into account the electron occupation in the conduction band, the bandgap narrowing, and band tails. The electron Fermi levels are used to determine the free electron concentrations, and we infer nanowire doping of 6 × 1017 to 1 × 1018 cm-3. These results show that cathodoluminescence provides a robust way to probe carrier concentrations in semiconductors with the possibility of mapping spatial inhomogeneities at the nanoscale.

Class-A operation of an optically-pumped 1.6 µm-emitting quantum dash-based vertical-external-cavity surface-emitting laser on InP.

A continuous-wave 1.6 µm-emitting InAs Quantum Dash-based Optically-Pumped Vertical-External-Cavity Surface-Emitting Laser on InP is demonstrated. The laser emits in the L-band with a stable linear polarization. Up to 163 mW output power has been obtained in multi-transverse mode regime. Single-frequency regime is achieved in the 1609-1622 nm range, with an estimated linewidth of 22 kHz in a 49 mm cavity, and a maximum emitted power of 7.9 mW at 1611 nm. In such conditions, the laser exhibits a Class-A behavior, with a cut-off frequency of 800 kHz and a shot-noise floor of -158 dB/Hz for 2 mA of detected photocurrent.

Shiba Bound States across the Mobility Edge in Doped InAs Nanowires.

We present a study of Andreev quantum dots fabricated with small-diameter (30 nm) Si-doped InAs nanowires where the Fermi level can be tuned across a mobility edge separating localized states from delocalized states. The transition to the insulating phase is identified by a drop in the amplitude and width of the excited levels and is found to have remarkable consequences on the spectrum of superconducting subgap resonances. While at deeply localized levels only quasiparticle cotunneling is observed, for slightly delocalized levels Shiba bound states form and a parity-changing quantum phase transition is identified by a crossing of the bound states at zero energy. Finally, in the metallic regime, single Andreev resonances are observed.

Sharpening the Interfaces of Axial Heterostructures in Self-Catalyzed AlGaAs Nanowires: Experiment and Theory.

The growth of III-III-V axial heterostructures in nanowires via the vapor-liquid-solid method is deemed to be unfavorable because of the high solubility of group III elements in the catalyst droplet. In this work, we study the formation by molecular beam epitaxy of self-catalyzed GaAs nanowires with AlxGa1-xAs insertions. The composition profiles are extracted and analyzed with monolayer resolution using high-angle annular dark-field scanning transmission electron microscopy. We test successfully several growth procedures to sharpen the heterointerfaces. For a given nanowire geometry, prefilling the droplet with Al atoms is shown to be the most efficient way to reduce the width of the GaAs/AlxGa1-xAs interface. Using the thermodynamic data available in the literature, we develop numerical and analytical models of the composition profiles, showing very good agreement with experiments. These models suggest that atomically sharp interfaces are attainable for catalyst droplets of small volumes.

Photon Cascade from a Single Crystal Phase Nanowire Quantum Dot.

We report the first comprehensive experimental and theoretical study of the optical properties of single crystal phase quantum dots in InP nanowires. Crystal phase quantum dots are defined by a transition in the crystallographic lattice between zinc blende and wurtzite segments and therefore offer unprecedented potential to be controlled with atomic layer accuracy without random alloying. We show for the first time that crystal phase quantum dots are a source of pure single-photons and cascaded photon-pairs from type II transitions with excellent optical properties in terms of intensity and line width. We notice that the emission spectra consist often of two peaks close in energy, which we explain with a comprehensive theory showing that the symmetry of the system plays a crucial role for the hole levels forming hybridized orbitals. Our results state that crystal phase quantum dots have promising quantum optical properties for single photon application and quantum optics.

Epitaxy of GaN Nanowires on Graphene.

Epitaxial growth of GaN nanowires on graphene is demonstrated using molecular beam epitaxy without any catalyst or intermediate layer. Growth is highly selective with respect to silica on which the graphene flakes, grown by chemical vapor deposition, are transferred. The nanowires grow vertically along their c-axis and we observe a unique epitaxial relationship with the ⟨21̅1̅0⟩ directions of the wurtzite GaN lattice parallel to the directions of the carbon zigzag chains. Remarkably, the nanowire density and height decrease with increasing number of graphene layers underneath. We attribute this effect to strain and we propose a model for the nanowire density variation. The GaN nanowires are defect-free and they present good optical properties. This demonstrates that graphene layers transferred on amorphous carrier substrates is a promising alternative to bulk crystalline substrates for the epitaxial growth of high quality GaN nanostructures.

Abrupt GaP/GaAs Interfaces in Self-Catalyzed Nanowires.

We achieve the self-catalyzed growth of pure GaP nanowires and GaAs1-xPx/GaAs1-yPy nanowire heterostructures by solid-source molecular beam epitaxy. Consecutive segments of nearly pure GaAs and GaP are fabricated by commuting the group V fluxes. We test different flux switching procedures and measure the corresponding interfacial composition profiles with atomic resolution using high-angle annular dark field scanning transmission electron microscopy. Interface abruptness is drastically improved by switching off all the molecular beam fluxes for a short time at the group V commutation. Finally, we demonstrate that the morphology of the growth front can be either flat or truncated, depending on the growth conditions. The method presented here allows for the facile synthesis of high quality GaP/GaAs axial heterostructures directly on Si (111) wafers.

Optical polarization properties of InAs/InP quantum dot and quantum rod nanowires.

The emission polarization of single InAs/InP quantum dot (QD) and quantum rod (QR) nanowires is investigated at room temperature. Whereas the emission of the QRs is mainly polarized parallel to the nanowire axis, the opposite behavior is observed for the QDs. These optical properties can be explained by a combination of dielectric effects related to the nanowire geometry and to the configuration of the valence band in the nanostructure. A theoretical model and finite difference in time domain calculations are presented to describe the impact of the nanowire and the surroundings on the optical properties of the emitter. Using this model, the intrinsic degree of linear polarization of the two types of emitters is extracted. The strong polarization anisotropies indicate a valence band mixing in the QRs but not in the QDs.

Record pure zincblende phase in GaAs nanowires down to 5 nm in radius.

We report the Au catalyst-assisted synthesis of 20 µm long GaAs nanowires by the vapor-liquid-solid hydride vapor phase epitaxy (HVPE) exhibiting a polytypism-free zincblende phase for record radii lower than 15 nm down to 5 nm. HVPE makes use of GaCl gaseous growth precursors at high mass input of which fast dechlorination at the usual process temperature of 715 °C results in high planar growth rate (standard 30-40 µm/h). When it comes to the vapor-liquid-solid growth of nanowires, fast solidification at a rate higher than 100 µm/h is observed. Nanowire growth by HVPE only proceeds by introduction of precursors in the catalyst droplets from the vapor phase. This promotes almost pure axial growth leading to nanowires with a constant cylinder shape over unusual length. The question of the cubic zincblende structure observed in HVPE-grown GaAs nanowires regardless of their radius is at the heart of the paper. We demonstrate that the vapor-liquid-solid growth in our conditions takes place at high liquid chemical potential that originates from very high influxes of both As and Ga. This yields a Ga concentration systematically higher than 0.62 in the Au-Ga-As droplets. The high Ga concentration decreases the surface energy of the droplets, which disables nucleation at the triple phase line thus preventing the formation of wurtzite structure whatever the nanowire radius is.

Class-A dual-frequency VECSEL at telecom wavelength.

We report class-A dual-frequency oscillation at 1.55 µm in a vertical external cavity surface emitting laser with more than 100 mW optical power. The two orthogonal linear polarizations of different frequencies oscillate simultaneously as their nonlinear coupling is reduced below unity by spatially separating them inside the active medium. The spectral behavior of the radio frequency beatnote obtained by optically mixing two polarizations and the phase noise of the beatnote have been explored for different coupling strengths between the lasing modes.

Growth of vertical GaAs nanowires on an amorphous substrate via a fiber-textured Si platform.

We demonstrate the vertical self-catalyzed molecular beam epitaxy (MBE) growth of GaAs nanowires on an amorphous SiO2 substrate by using a smooth [111] fiber-textured silicon thin film with very large grains, fabricated by aluminum-induced crystallization. This generic platform paves the way to the use of inexpensive substrates for the fabrication of dense ensembles of vertically standing nanowires (NWs) with promising perspectives for the integration of NWs in devices.