George Immink

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.

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.

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.

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.

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.

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.

Periodic nanowire structures

We show control of the crystal structure of indium phosphide (InP) and gallium phosphide (GaP) nanowires by impurity dopants. More importantly, we demonstrate that we can, once we have enforced the zinc blende crystal structure, induce twinning superlattices with long-range order in the length direction in the nanowires. The spacing of the superlattices is tuned by the wire diameter and the zinc dopant concentration. These findings have been quantitatively modelled based on the cross-sectional shape of the zinc-blende nanowires.

Correlated twins in nanowires

Semiconducting nanowires offer the possibility of nearly unlimited complex bottom-up design which allows for new device concepts. The control in defects (i.e. twin planes) and the crystal structure are crucial for an optimal device performance. Normally twin planes occur randomly during growth, leading to imperfection in the crystal quality of the nanowire, resulting in electronic and optical barriers.

Towards vertical III-V nanowire devices

Investigation and understanding of growth parameters determining nanowire growth rates is necessary. For vertical architecture design relying on closely-spaced nanowire-based devices, absolute control of growth rates and wire (device) dimensions is required. Heterostructured nanowires where the segment dimensions critically determine quantization effects and thus the (opto) electronic properties of the wires were synthesized.