Twinning superlattices in indium phosphide nanowires.

Semiconducting nanowires offer the possibility of nearly unlimited complex bottom-up design, which allows for new device concepts. However, essential parameters that determine the electronic quality of the wires, and which have not been controlled yet for the III-V compound semiconductors, are the wire crystal structure and the stacking fault density. In addition, a significant feature would be to have a constant spacing between rotational twins in the wires such that a twinning superlattice is formed, as this is predicted to induce a direct bandgap in normally indirect bandgap semiconductors, such as silicon and gallium phosphide. Optically active versions of these technologically relevant semiconductors could have a significant impact on the electronics and optics industry. Here we show first that we can control the crystal structure of indium phosphide (InP) nanowires by using impurity dopants. We have found that zinc decreases the activation barrier for two-dimensional nucleation growth of zinc-blende InP and therefore promotes crystallization of the InP nanowires in the zinc-blende, instead of the commonly found wurtzite, crystal structure. More importantly, we then demonstrate that we can, once we have enforced the zinc-blende crystal structure, induce twinning superlattices with long-range order in InP nanowires. We can tune the spacing of the superlattices by changing the wire diameter and the zinc concentration, and we present a model based on the distortion of the catalyst droplet in response to the evolution of the cross-sectional shape of the nanowires to quantitatively explain the formation of the periodic twinning.

High optical quality single crystal phase wurtzite and zincblende InP nanowires.

We report single crystal phase and non-tapered wurtzite (WZ) and zincblende twinning superlattice (ZB TSL) InP nanowires (NWs). The NWs are grown in a metalorganic vapor phase epitaxy (MOVPE) reactor using the vapor-liquid-solid (VLS) mechanism and in situ etching with HCl at a high growth temperature. Our stacking fault-free WZ and ZB TSL NWs allow access to the fundamental properties of both NW crystal structures, whose optical and electronic behaviors are often screened by polytypism or incorporated impurities. The WZ NWs show no acceptor-related emission, implying that the VLS-grown NW is almost free of impurities due to sidewall removal by HCl. They only emit light at the free exciton (1.491 eV) and the donor bound exciton transition (1.4855 eV). The ZB NWs exhibit a photoluminescence spectrum being unaffected by the twinning planes. Surprisingly, the acceptor-related emission in the ZB NWs can be almost completely removed by etching away the impurity-contaminated sidewall grown via a vapor-solid mechanism.

From InSb nanowires to nanocubes: looking for the sweet spot.

High aspect ratios are highly desired to fully exploit the one-dimensional properties of indium antimonide nanowires. Here we systematically investigate the growth mechanisms and find parameters leading to long and thin nanowires. Variation of the V/III ratio and the nanowire density are found to have the same influence on the "local" growth conditions and can control the InSb shape from thin nanowires to nanocubes. We propose that the V/III ratio controls the droplet composition and the radial growth rate and these parameters determine the nanowire shape. A sweet spot is found for nanowire interdistances around 500 nm leading to aspect ratios up to 35. High electron mobilities up to 3.5 × 10(4) cm(2) V(-1) s(-1) enable the realization of complex spintronic and topological devices.

The role of surface energies and chemical potential during nanowire growth.

We present an approach to quantitatively determine the magnitudes and the variation of the chemical potential in the droplet (Δµ), the solid-liquid (γ(SL)) and the liquid-vapor (γ(LV)) interface energies upon variation of the group III partial pressure during vapor-liquid-solid-growth of nanowires. For this study, we use GaP twinning superlattice nanowires. We show that γ(LV) is the quantity that is most sensitive to the Ga partial pressure (p(Ga)), its dependence on p(Ga) being three to four times as strong as that of γ(SL) or Δµ, and that as a consequence the surface energies are as important in determining the twin density as the chemical potential. This unexpected result implies that surfactants could be used during nanowire growth to engineer the nanowire defect structure and crystal structure.

Crystal structure transfer in core/shell nanowires.

Structure engineering is an emerging tool to control opto-electronic properties of semiconductors. Recently, control of crystal structure and the formation of a twinning superlattice have been shown for III-V nanowires. This level of control has not been obtained for Si nanowires, the most relevant material for the semiconductor industry. Here, we present an approach, in which a designed twinning superlattice with the zinc blende crystal structure or the wurtzite crystal structure is transferred from a gallium phosphide core wire to an epitaxially grown silicon shell. These materials have a difference in lattice constants of only 0.4%, which allows for structure transfer without introducing extra defects. The twinning superlattices, periodicity, and shell thickness can be tuned with great precision. Arrays of free-standing Si nanotubes are obtained by a selective wet-chemical etch of the core wire.

Paired twins and [112] morphology in GaP nanowires.

Formation of random as well as periodic planar defects can occur during vapor-liquid-solid growth of nanowires with the zinc-blende crystal structure. Here we investigate the formation of pairs of twin planes in GaP nanowires. In such pairs, the first twin plane is formed at a random position, rapidly followed by the formation of a second twin plane of which the position is directly related to that of the first one. We show that the triangular [112] morphology of the nanowire is a key element in the formation of these twin pairs. We have extended our previous kinetic nucleation model and show that this describes the development of the nanowire morphology and its relation with the formation of single and paired twin planes.

Generic nano-imprint process for fabrication of nanowire arrays.

A generic process has been developed to grow nearly defect-free arrays of (heterostructured) InP and GaP nanowires. Soft nano-imprint lithography has been used to pattern gold particle arrays on full 2 inch substrates. After lift-off organic residues remain on the surface, which induce the growth of additional undesired nanowires. We show that cleaning of the samples before growth with piranha solution in combination with a thermal anneal at 550 degrees C for InP and 700 degrees C for GaP results in uniform nanowire arrays with 1% variation in nanowire length, and without undesired extra nanowires. Our chemical cleaning procedure is applicable to other lithographic techniques such as e-beam lithography, and therefore represents a generic process.

Zinc incorporation via the vapor-liquid-solid mechanism into InP nanowires.

We report the incorporation of zinc atoms into vapor-liquid-solid grown indium phosphide nanowires via a gold catalyst particle. We demonstrate this by synthesizing axial pn-junctions, chemically etching them, and fabricating electrical contacts in a vertical configuration. Electrical measurements show clear diode behavior. Control of dopant incorporation is crucial for future applications and will eventually lead to full freedom of design.

Formation and electronic properties of InSb nanocrosses.

Signatures of Majorana fermions have recently been reported from measurements on hybrid superconductor-semiconductor nanowire devices. Majorana fermions are predicted to obey special quantum statistics, known as non-Abelian statistics. To probe this requires an exchange operation, in which two Majorana fermions are moved around one another, which requires at least a simple network of nanowires. Here, we report on the synthesis and electrical characterization of crosses of InSb nanowires. The InSb wires grow horizontally on flexible vertical stems, allowing nearby wires to meet and merge. In this way, near-planar single-crystalline nanocrosses are created, which can be measured by four electrical contacts. Our transport measurements show that the favourable properties of the InSb nanowire devices-high carrier mobility and the ability to induce superconductivity--are preserved in the cross devices. Our nanocrosses thus represent a promising system for the exchange of Majorana fermions.

Growth and optical properties of axial hybrid III-V/silicon nanowires.

Hybrid silicon nanowires with an integrated light-emitting segment can significantly advance nanoelectronics and nanophotonics. They would combine transport and optical characteristics in a nanoscale device, which can operate in the fundamental single-electron and single-photon regime. III-V materials, such as direct bandgap gallium arsenide, are excellent candidates for such optical segments. However, interfacing them with silicon during crystal growth is a major challenge, because of the lattice mismatch, different expansion coefficients and the formation of antiphase boundaries. Here we demonstrate a silicon nanowire with an integrated gallium-arsenide segment. We precisely control the catalyst composition and surface chemistry to obtain dislocation-free interfaces. The integration of gallium arsenide of high optical quality with silicon is enabled by short gallium phosphide buffers. We anticipate that such hybrid silicon/III-V nanowires open practical routes for quantum information devices, where for instance electronic and photonic quantum bits are manipulated in a III-V segment and stored in a silicon section.

Synergetic nanowire growth.

Interest in nanowires continues to grow because they hold the promise of monolithic integration of high-performance semiconductors with new functionality into existing silicon technology. Most nanowires are grown using vapour-liquid-solid growth, and despite many years of study this growth mechanism remains under lively debate. In particular, the role of the metal particle is unclear. For instance, contradictory results have been reported on the effect of particle size on nanowire growth rate. Additionally, nanowire growth from a patterned array of catalysts has shown that small wire-to-wire spacing leads to materials competition and a reduction in growth rates. Here, we report on a counterintuitive synergetic effect resulting in an increase of the growth rate for decreasing wire-to-wire distance. We show that the growth rate is proportional to the catalyst area fraction. The effect has its origin in the catalytic decomposition of precursors and is applicable to a variety of nanowire materials and growth techniques.

Three-dimensional morphology of GaP-GaAs nanowires revealed by transmission electron microscopy tomography.

We have investigated the morphology of heterostructured GaP-GaAs nanowires grown by metal-organic vapor-phase epitaxy as a function of growth temperature and V/III precursor ratio. The study of heterostructured nanowires with transmission electron microscopy tomography allowed the three-dimensional morphology to be resolved, and discrimination between the effect of axial (core) and radial (shell) growth on the morphology. A temperature- and precursor-dependent structure diagram for the GaP nanowire core morphology and the evolution of the different types of side facets during GaAs and GaP shell growth were constituted.

Interface study on heterostructured GaP-GaAs nanowires.

The interface chemical composition of heterostructured GaP-GaAs nanowire segments was studied by the use of energy-dispersive x-ray analysis. An arsenic-rich tail in the GaP segments following GaAs could be minimized by reducing the AsH(3) molar fraction and the growth rate. For the temperature regime used for vapour-liquid-solid growth, we observe the opposite trend on interface sharpness compared to high-temperature layer-by-layer growth, that is, the sharpness of the interface improves with reducing temperature.

Growth kinetics of heterostructured GaP-GaAs nanowires.

We have studied the vapor-liquid-solid (VLS) growth dynamics of GaP and GaAs in heterostructured GaP-GaAs nanowires. The wires containing multiple GaP-GaAs junctions were grown by the use of metal-organic vapor phase-epitaxy (MOVPE) on SiO(2), and the lengths of the individual sections were obtained from transmission electron microscopy. The growth kinetics has been studied as a function of temperature and the partial pressures of the precursors. We found that the growth of the GaAs sections is limited by the arsine (AsH(3)) as well as the trimethylgallium (Ga(CH(3))(3)) partial pressures, whereas the growth of GaP is a temperature-activated, phosphine(PH(3))-limited process with an activation energy of 115 +/- 6 kJ/mol. The PH(3) kinetics obeys the Hinshelwood-Langmuir mechanism, indicating that the dissociation reaction of adsorbed PH(3) into PH(2) and H on the catalytic gold surface is the rate-limiting step for the growth of GaP. In addition, we have studied the competitive thin layer growth on the sidewalls of the nanowires. Although the rate of this process is 2 orders of magnitude lower than the growth rate of the VLS mechanism, it competes with VLS growth and results in tapered nanowires at elevated temperatures.