Role of thermodynamics and kinetics in the composition of ternary III-V nanowires

We explain the composition of ternary nanowires nucleating from a quaternary liquid melt. The model we derive describes the evolution of the solid composition from the nucleated-limited composition to the kinetic one. The effect of the growth temperature, group V concentration and Au/III concentration ratio on the solid-liquid dependence is studied. It has been shown that the solid composition increases with increasing temperature and Au concentration in the droplet at the fixed In/Ga concentration ratio. The model does not depend on the site of nucleation and the geometry of monolayer growth and is applicable for nucleation and growth on a facet with finite radius. The case of a steady-state (or final) solid composition is considered and discussed separately. While the nucleation-limited liquid-solid composition dependence contains the miscibility gap at relevant temperatures for growth of InxGa1-xAs NWs, the miscibility gap may be suppressed completely in the steady-state growth regime at high supersaturation. The theoretical results are compared with available experimental data via the combination of the here described solid-liquid and a simple kinetic liquid-vapor model

Zinc blende and wurtzite crystal structure formation in gold catalyzed InGaAs nanowires

III-V semiconductor nanowires made of materials which have the zinc blende crystal structure in bulk are well known to exhibit either the zinc blende or the wurtzite crystal structure. Understanding and controlling which crystal structure that forms is of highest importance for nanowire applications in a variety of areas. In addition to this, composition control in ternary nanowires is another key technology area for successful nanowire applications. We derive a general model, based on two-component nucleation theory, which we use to explain the so far less understood experimental observations of zinc blende, wurtzite, and mixed crystal structure as a function of growth conditions and composition, x, in gold catalyzed InxGa1-xAs nanowires. An interesting theoretical finding is that the wurtzite and zinc blende phases have different compositions, even if they are nucleated from the same catalyst particle at the same conditions

Surface energy driven miscibility gap suppression during nucleation of III-V ternary alloys

The existence of a miscibility gap limits the range of solid compositions which are possible to achieve under near-equilibrium growth conditions. Circumventing the miscibility gap is of paramount importance for device fabrication. We propose that one of the suppression mechanisms is the nucleus surface energy and explain how the surface energy influences the miscibility gap during nucleation from a liquid melt. By doing this, we start with the formation of the critical nucleus of a ternary alloy considering its surface energy as a combination of the binary ones. For certain nucleation scenarios in the InGaAs materials system we show that the compositional independence of the surface energy term is a good approximation due to similar values for InAs and GaAs pairs. However, a large difference in the surface energies of the two materials may lead to a significant modification of the liquid-solid composition dependence and a complete suppression of the miscibility gap

Modeling the Radial Growth of Self-Catalyzed III-V Nanowires

A new model for the radial growth of self-catalyzed III-V nanowires on different substrates is presented, which describes the nanowire morphological evolution without any free parameters. The model takes into account the re-emission of group III atoms from a mask surface and the shadowing effect in directional deposition techniques such as molecular beam epitaxy. It is shown that radial growth is faster for larger pitches of regular nanowire arrays or lower surface density, and can be suppressed by increasing the V/III flux ratio or decreasing re-emission. The model describes quite well the data on the morphological evolution of Ga-catalyzed GaP and GaAs nanowires on different substrates, where the nanowire length increases linearly and the radius enlarges sub-linearly with time. The obtained analytical expressions and numerical data should be useful for morphological control over different III-V nanowires in a wide range of growth conditions

Assembling your nanowire : An overview of composition tuning in ternary III-V nanowires

The ability to grow defect-free nanowires in lattice-mismatched material systems and to design their properties has made them ideal candidates for applications in fields as diverse as nanophotonics, nanoelectronics and medicine. After studying nanostructures consisting of elemental and binary compound semiconductors, scientists turned their attention to more complex systems - ternary nanowires. Composition control is key in these nanostructures since it enables bandgap engineering. The use of different combinations of compounds and different growth methods has resulted in numerous investigations. The aim of this review is to present a survey of the material systems studied to date, and to give a brief overview of the issues tackled and the progress achieved in nanowire composition tuning. We focus on ternary III x III1-x V nanowires (AlGaAs, AlGaP, AlInP, InGaAs, GaInP and InGaSb) and IIIV x V1-x nanowires (InAsP, InAsSb, InPSb, GaAsP, GaAsSb and GaSbP)

Nucleation-limited composition of ternary III-V nanowires forming from quaternary gold based liquid alloys

We derive an analytic expression for the composition of a ternary solid material nucleating from a quaternary liquid melt. The calculations are based on the two-component nucleation theory with realistic descriptions of the liquid and solid phases. We apply this theory to gold-catalyzed, nucleation limited vapor-liquid-solid growth of ternary III-V nanowires. We consider ternary gallium, indium, and aluminum arsenides and antimonides and discuss growth conditions for optimum composition control in these materials. Furthermore, we compare our calculations with the results of an equilibrium thermodynamic model

Geometrical Selection of GaN Nanowires Grown by Plasma-Assisted MBE on Polycrystalline ZrN Layers

GaN nanowires grown on metal substrates have attracted increasing interest for a wide range of applications. Herein, we report GaN nanowires grown by plasma-assisted molecular beam epitaxy on thin polycrystalline ZrN buffer layers, sputtered onto Si(111) substrates. The nanowire orientation was studied by X-ray diffraction and scanning electron microscopy, and then described within a model as a function of the Ga beam angle, nanowire tilt angle, and substrate rotation. We show that vertically aligned nanowires grow faster than inclined nanowires, which leads to an interesting effect of geometrical selection of the nanowire orientation in the directional molecular beam epitaxy technique. After a given growth time, this effect depends on the nanowire surface density. At low density, the nanowires continue to grow with random orientations as nucleated. At high density, the effect of preferential growth induced by the unidirectional supply of the material in MBE starts to dominate. Faster growing nanowires with smaller tilt angles shadow more inclined nanowires that grow slower. This helps to obtain more regular ensembles of vertically oriented GaN nanowires despite their random position induced by the metallic grains at nucleation. The obtained dense ensembles of vertically aligned GaN nanowires on ZrN/Si(111) surfaces are highly relevant for device applications. Importantly, our results are not specific for GaN nanowires on ZrN buffers, and should be relevant for any nanowires that are epitaxially linked to the randomly oriented surface grains in the directional molecular beam epitaxy

Compositional Correlation between the Nanoparticle and the Growing Au-Assisted InxGa1-xAs Nanowire

The nanowire geometry is favorable for the growth of ternary semiconductor materials, because the composition and properties can be tuned freely without substrate lattice matching. To achieve precise control of the composition in ternary semiconductor nanowires, a deeper understanding of the growth is required. One unknown aspect of seeded nanowire growth is how the composition of the catalyst nanoparticle affects the resulting composition of the growing nanowire. We report the first in situ measurements of the nanoparticle and InxGa1-xAs nanowire compositional relationship using an environmental transmission electron microscopy setup. The compositions were measured and correlated during growth, via X-ray energy dispersive spectroscopy. Contrary to predictions from thermodynamic models, the experimental results do not show a miscibility gap. Therefore, we construct a kinetic model that better predicts the compositional trends by suppressing the miscibility gap. The findings imply that compositional control of InxGa1-xAs nanowires is possible across the entire compositional range

Tapering-free monocrystalline Ge nanowires synthesized via plasma-assisted VLS using in and Sn catalysts

In and Sn are the type of catalysts which do not introduce deep level electrical defects within the bandgap of germanium (Ge). However, Ge nanowires produced using these catalysts usually have a large diameter, a tapered morphology, and mixed crystalline and amorphous phases. In this study, we show that plasma-assisted vapor-liquid-solid (PA-VLS) method can be used to synthesize Ge nanowires. Moreover, at certain parameter domains, the sidewall deposition issues of this synthesis method can be avoided and long, thin tapering-free monocrystalline Ge nanowires can be obtained with In and Sn catalysts. We find two quite different parameter domains where Ge nanowire growth can occur via PA-VLS using In and Sn catalysts: (i) a low temperature-low pressure domain, below ∼235 °C at a GeH4 partial pressure of ∼6 mTorr, where supersaturation in the catalyst occurs thanks to the low solubility of Ge in the catalysts, and (ii) a high temperature-high pressure domain, at ∼400 °C and a GeH4 partial pressure above ∼20 mTorr, where supersaturation occurs thanks to the high GeH4 concentration. While growth at 235 °C results in tapered short wires, operating at 400 °C enables cylindrical nanowire growth. With the increase of growth temperature, the crystalline structure of the nanowires changes from multi-crystalline to mono-crystalline and their growth rate increases from ∼0.3 nm s-1 to 5 nm s-1. The cylindrical Ge nanowires grown at 400°C usually have a length of few microns and a radius of around 10 nm, which is well below the Bohr exciton radius in bulk Ge (24.3 nm). To explain the growth mechanism, a detailed growth model based on the key chemical reactions is provided

Te incorporation and activation as n-type dopant in self-catalyzed GaAs nanowires

Dopant atoms can be incorporated into nanowires either via the vapor-liquid-solid mechanism through the catalyst droplet or by the vapor-solid growth on the sidewalls. Si is a typical n-type dopant for GaAs, but in nanowires it often suffers from a strongly amphoteric nature in the vapor-liquid-solid process. This issue can be avoided by using Te, which is a promising but less common alternative for n-type doping of GaAs nanowires. Here, we present a detailed investigation of Te-doped self-catalyzed GaAs nanowires. We use several complementary experimental techniques, such as atom probe tomography, off-axis electron holography, micro-Raman spectroscopy, and single-nanowire transport characterization, to assess the Te concentration, the free-electron concentration, and the built-in potential in Te-doped GaAs nanowires. By combing the experimental results with a theoretical model, we show that Te atoms are mainly incorporated by the vapor-liquid-solid process through the Ga droplet, which leads to both axial and radial dopant gradients due to Te diffusion inside the nanowires and competition between axial elongation and radial growth of nanowires. Furthermore, by comparing the free-electron concentration from Raman spectroscopy and the Te-atom concentrations from atom probe tomography, we show that the activation of Te donor atoms is 100% at a doping level of 4×1018cm-3, which is a significant result in terms of future device applications