Selective area epitaxy of GaAs: the unintuitive role of feature size and pitch.

Selective area epitaxy (SAE) provides the path for scalable fabrication of semiconductor nanostructures in a device-compatible configuration. In the current paradigm, SAE is understood as localized epitaxy, and is modelled by combining planar and self-assembled nanowire growth mechanisms. Here we use GaAs SAE as a model system to provide a different perspective. First, we provide evidence of the significant impact of the annealing stage in the calculation of the growth rates. Then, by elucidating the effect of geometrical constraints on the growth of the semiconductor crystal, we demonstrate the role of adatom desorption and resorption beyond the direct-impingement and diffusion-limited regime. Our theoretical model explains the effect of these constraints on the growth, and in particular why the SAE growth rate is highly sensitive to the pattern geometry. Finally, the disagreement of the model at the largest pitch points to non-negligible multiple adatom recycling between patterned features. Overall, our findings point out the importance of considering adatom diffusion, adsorption and desorption dynamics in designing the SAE pattern to create pre-determined nanoscale structures across a wafer. These results are fundamental for the SAE process to become viable in the semiconductor industry.

Regulated Dynamics with Two Monolayer Steps in Vapor-Solid-Solid Growth of Nanowires.

The growth of ZnTe nanowires and ZnTe-CdTe nanowire heterostructures is studied by in situ transmission electron microscopy. We describe the shape and the change of shape of the solid gold nanoparticle during vapor-solid-solid growth. We show the balance between one monolayer and two monolayer steps, which characterizes the vapor-liquid-solid and vapor-solid-solid growth modes of ZnTe. We discuss the likely role of the mismatch strain and lattice coincidence between gold and ZnTe on the predominance of two monolayer steps during vapor-solid-solid growth and on the subsequent self-regulation of the step dynamics. Finally, the formation of an interface between CdTe and ZnTe is described.

Stable and high yield growth of GaP and In0.2Ga0.8As nanowire arrays using In as a catalyst.

We report the first investigation of indium (In) as the vapor-liquid-solid catalyst of GaP and InGaAs nanowires by molecular beam epitaxy. A strong asymmetry in the Ga distribution between the liquid and solid phases allows one to obtain pure GaP and In0.2Ga0.8As nanowires while the liquid catalyst remains nearly pure In. This uncommon In catalyst presents several advantages. First, the nanowire morphology can be tuned by changing the In flux alone, independently of the Ga and group V fluxes. Second, the nanowire crystal structure always remains cubic during steady state growth and catalyst crystallization, despite the low contact angle of the liquid droplet measured after growth (95°). Third, the vertical yield of In-catalyzed GaP and (InGa)As nanowire arrays on patterned silicon substrates increases dramatically. Combining straight sidewalls, controllable morphologies and a high vertical yield, In-catalysts provide an alternative to the standard Au or Ga alloys for the bottom-up growth of large scale homogeneous arrays of (InGa)As or GaP nanowires.

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.

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.

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.

Energy harvesting efficiency in GaN nanowire-based nanogenerators: the critical influence of the Schottky nanocontact.

The performances of 1D-nanostructure based nanogenerators are governed by the ability of nanostructures to efficiently convert mechanical deformation into electrical energy, and by the efficiency with which this piezo-generated energy is harvested. In this paper, we highlight the crucial influence of the GaN nanowire-metal Schottky nanocontact on the energy harvesting efficiency. Three different metals, p-type doped diamond, PtSi and Pt/Ir, have been investigated. By using an atomic force microscope equipped with a Resiscope module, we demonstrate that the harvesting of piezo-generated energy is up to 2.4 times more efficient using a platinum-based Schottky nanocontact compared to a doped diamond-based nanocontact. In light of Schottky contact characteristics, we evidence that the conventional description of the Schottky diode cannot be applied. The contact is governed by its nanometer size. This specific behaviour induces notably a lowering of the Schottky barrier height, which gives rise to an enhanced conduction. We especially demonstrate that this effective thinning is directly correlated with the improvement of the energy harvesting efficiency, which is much pronounced for Pt-based Schottky diodes. These results constitute a building block to the overall improvement of NW-based nanogenerator devices.

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.

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.

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.

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.

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.

Nucleation antibunching in catalyst-assisted nanowire growth.

We elaborate InP(1-xA)s(x) nanowires by vapor-liquid-solid growth, with small and short composition oscillations produced on purpose with a constant time period. The lengths of these oscillations, measured in single wires by transmission electron microscopy, give access to instantaneous growth rates and their distribution reveals the nucleation statistics. We find that these statistics are strongly sub-Poissonian, which proves that the nucleation events are anticorrelated in time. This effect, specific to nanovolumes, efficiently regulates nanowire growth. We explain it by the rapid depletion of the catalyst droplet in group V atoms upon forming each monolayer of the nanowire.

Wurtzite to zinc blende phase transition in GaAs nanowires induced by epitaxial burying.

We bury vertical free-standing core-shell GaAs/AlGaAs nanowires by a planar GaAs overgrowth. As the nanowires get buried, their crystalline structure progressively transforms: whereas the upper emerging part retains its initial wurtzite structure, the buried part adopts the zinc blende structure of the burying layer. The burying process also suppresses all the stacking faults that existed in the wurtzite nanowires. We consider two possible mechanisms for the structural transition upon burying, examine how they can be discriminated from each other, and explain why the transition is favorable.

Why does wurtzite form in nanowires of III-V zinc blende semiconductors?

We develop a nucleation-based model to explain the formation of the wurtzite phase during the catalyzed growth of freestanding nanowires of zinc blende semiconductors. We show that in vapor-liquid-solid nanowire growth, nucleation generally occurs preferentially at the triple phase line. This entails major differences between zinc blende and wurtzite nuclei. Depending on the pertinent interface energies, wurtzite nucleation is favored at high liquid supersaturation. This explains our systematic observation of zinc blende during early growth of gold-catalyzed GaAs nanowires.