Rienk E. Algra

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.

Design of Light Scattering in Nanowire Materials for Photovoltaic Applications

We experimentally investigate the optical properties of layers of InP, Si, and GaP nanowires, relevant for applications in solar cells. The nanowires are strongly photonic, resulting in a significant coupling mismatch with incident light due to multiple scattering. We identify a design principle for the effective suppression of reflective losses, based on the ratio of the nondiffusive absorption and diffusive scattering lengths. Using this principle, we demonstrate successful suppression of the hemispherical diffuse reflectance of InP nanowires to below that of the corresponding transparent effective medium. The design of light scattering in nanowire materials is of large importance for optimization of the external efficiency of nanowire-based photovoltaic devices.

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.

Large Photonic Strength of Highly Tunable Resonant Nanowire Materials

We demonstrate that highly tunable nanowire arrays with optimized diameters, volume fractions, and alignment form one of the strongest optical scattering materials to date. Using a new broad-band technique, we explore the scattering strength of the nanowires by varying systematically their diameter and alignment on the substrate. We identify strong Mie-type internal resonances of the nanowires which can be tuned over the entire visible spectrum. The tunability of nanowire materials opens up exciting new prospects for fundamental and applied research ranging from random lasers to solar cells, exploiting the extreme scattering strength, internal resonances, and preferential alignment of the nanowires. Although we have focused our investigation on gallium phosphide nanowires, the results can be universally applied to other types of group III-V, II-VI, or IV nanowires.

Nanoscale free-carrier profiling of individual semiconductor nanowires by infrared near-field nanoscopy

We report quantitative, noninvasive and nanoscale-resolved mapping of the free-carrier distribution in InP nanowires with doping modulation along the axial and radial directions, by employing infrared near-field nanoscopy. Owing to the techniques capability of subsurface probing, we provide direct experimental evidence that dopants in interior nanowire shells effectively contribute to the local free-carrier concentration. The high sensitivity of s-SNOM also allows us to directly visualize nanoscale variations in the free-carrier concentration of wires as thin as 20 nm, which we attribute to local growth defects. Our results open interesting avenues for studying local conductivity in complex nanowire heterostructures, which could be further enhanced by near-field infrared nanotomography.

Surface passivated InAs/InP core/shell nanowires

We report the growth and characterization of InAs nanowires capped with a 0.5–1 nm epitaxial InP shell. The low-temperature field-effect mobility is increased by a factor 2–5 compared to bare InAs nanowires. We extract the highest low-temperature peak electron mobilities obtained for nanowires to this date, exceeding 20 000 cm2 V s?1. The electron density in the nanowires, determined at zero gate voltage, is reduced by an order of magnitude compared to uncapped InAs nanowires. For smaller diameter nanowires we find an increase in electron density, which can be related to the presence of an accumulation layer at the InAs/InP interface. However, compared to the surface accumulation layer in uncapped InAs, this electron density is much reduced. We suggest that the increase in the observed field-effect mobility can be attributed to an increase of conduction through the inner part of the nanowire and a reduction of the contribution of electrons from the low-mobility accumulation layer. Furthermore the shell around the InAs reduces the surface roughness scattering and ionized impurity scattering in the nanowire.

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.

Selective Excitation and Detection of Spin States in a Single Nanowire Quantum Dot

We report exciton spin memory in a single InAs(0.25)P(0.75) quantum dot embedded in an InP nanowire. By synthesizing clean quantum dots with linewidths as narrow as about 30 microeV, we are able to resolve individual spin states at magnetic fields on the order of 1 T. We can prepare a given spin state by tuning excitation polarization or excitation energy. These experiments demonstrate the potential of this system to form a quantum interface between photons and electrons.

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.