Механизм роста монослоя на верхней грани Ga-каталитических нитевидных нанокристаллов GaAs и GaP

The growth mechanism of monolayer on the top facet of Ga-catalyzed GaAs and GaP nanowires is investigated. Within the framework of a theoretical model, the maximal monolayer coverage due to the material in the catalyst droplet, the nanowire growth rate and the content of group V atoms in the droplet are found depending on the growth conditions. The estimates of the phosphorus re-evaporation coefficient from neighboring nanowires and substrate are obtained by comparing the theoretical and experimental growth rate of Ga-catalyzed GaP nanowires.

Self-consistent modeling of MBE self-catalyzed GaAs nanowire growth

Self-catalyzed GaAs nanowires are synthesized by molecular beam epitaxy at various arsenic fluxes and growth temperatures. The growth of GaAs nanowires is simulated considering the kinetics of material transport inside the catalyst droplet. The re-evaporation coefficient of arsenic is estimated for the given growth conditions. Calculated nanowire growth rate is in satisfactory agreement with the experimental data.

Post-nucleation evolution of the liquid-solid interface in nanowire growth

We study using in situ transmission electron microscopy the birth of GaAs nanowires from liquid Au-Ga catalysts on amorphous substrates. Lattice-resolved observations of the starting stages of growth are reported here for the first time. It reveals how the initial nanostructure evolves into a nanowire growing in a zincblende <111> or the equivalent wurtzite <0001> direction. This growth direction(s) is what is typically observed in most III-V and II-VI nanowires. However, the reason for this preferential nanowire growth along this direction is still a dilemma. Based on the videos recorded shortly after the nucleation of nanowires, we argue that the lower catalyst droplet-nanowire interface energy of the {111} facet when zincblende (or the equivalent {0001} facet in wurtzite) is the reason for this direction selectivity in nanowires.

Thermodynamics of the Vapor–Liquid–Solid Growth of Ternary III–V Nanowires in the Presence of Silicon

Based on a thermodynamic model, we quantify the impact of adding silicon atoms to a catalyst droplet on the nucleation and growth of ternary III–V nanowires grown via the self-catalyzed vapor–liquid–solid process. Three technologically relevant ternaries are studied: InGaAs, AlGaAs and InGaN. For As-based alloys, it is shown that adding silicon atoms to the droplet increases the nanowire nucleation probability, which can increase by several orders magnitude depending on the initial chemical composition of the catalyst. Conversely, silicon atoms are found to suppress the nucleation rate of InGaN nanowires of different compositions. These results can be useful for understanding and controlling the vapor–liquid–solid growth of ternary III–V nanowires on silicon substrates as well as their intentional doping with Si.

Oscillations of As Concentration and Electron-to-Hole Ratio in Si-Doped GaAs Nanowires

III–V nanowires grown by the vapor–liquid–solid method often show self-regulated oscillations of group V concentration in a catalyst droplet over the monolayer growth cycle. We investigate theoretically how this effect influences the electron-to-hole ratio in Si-doped GaAs nanowires. Several factors influencing the As depletion in the vapor–liquid–solid nanowire growth are considered, including the time-scale separation between the steps of island growth and refill, the “stopping effect” at very low As concentrations, and the maximum As concentration at nucleation and desorption. It is shown that the As depletion effect is stronger for slower nanowire elongation rates and faster for island growth relative to refill. Larger concentration oscillations suppress the electron-to-hole ratio and substantially enhance the tendency for the p-type Si doping of GaAs nanowires, which is a typical picture in molecular beam epitaxy. The oscillations become weaker and may finally disappear in vapor deposition techniques such as hydride vapor phase epitaxy, where the n-type Si doping of GaAs nanowires is more easily achievable.

Development of Growth Theory for Vapor–Liquid–Solid Nanowires: Wetting Scenario, Front Curvature, Growth Angle, Linear Tension, and Radial Instability

In this paper, we report that under wetting conditions (or modes) of nanowire (NW) growth, when a nonplanar crystallization front emerges under a catalyst droplet, a shift in the three-phase line (TPL) of the vapor–liquid–crystal interface occurs under thermodynamically stable conditions when the angle with respect to the droplet surface, termed the growth angle, is fixed. The growth angle of the NWs is determined not from a geometrical perspective but on the basis of the physical aspects of the processes occurring around the TPL, revealing a size dependence caused by the influence of linear tension of the three-phase contact of a vapor–liquid crystal. The observed radial periodic instability of the NWs is described according to the size dependence of the thermodynamic growth angle, which induces negative feedback in the system. Under the influence of linear tension and positive feedback, the tips or needles of NWs can be formed.

Crystal phase engineering of self-catalyzed GaAs nanowires using a RHEED diagram

It is well known that the crystalline structure of the III–V nanowires (NWs) is mainly controlled by the wetting contact angle of the catalyst droplet which can be tuned by the III and V flux.

Свободная энергия образования зародыша при росте III-V нитевидного нанокристалла

An expression for the free energy of forming an island from a catalyst droplet in the vapor-liquid-solid growth of III-V nanowires is obtained. The effect of the droplet depletion with its group V (As) content is studied in the presence of material influx from vapor. Different growth regimes of a nanowire monolayer are theoretically analyzed, including the regime with the stopping size under very low As concentrations in liquid. It is shown that the island stops growing when the As content in the droplet decreases to its equilibrium value. The obtained results should be useful for understanding and modeling the growth kinetics of III-V nanowires, their crystal phase, nucleation statistics and length distributions within the ensembles of nanowires as well as the doping process.

Влияние температуры на морфологию планарных нанопроволок GaAs (моделирование)

Using a kinetic lattice Monte Carlo model, the self-catalyzed growth of planar GaAs nanowires was analyzed. The nanowire growth via the vapor-liquid-crystal mechanism was considered. The effect of temperature and the catalyst droplet location on the morphology and growth direction of planar GaAs nanowires was studied. For GaAs(111)A and GaAs(111)B substrates, a temperature range corresponding to stable growth of planar GaAs nanowires was revealed. The special asymmetric arrangement of droplets allows the one-directional nanowire growth.

Кинетика роста планарных нитевидных нанокристаллов

A kinetic equation is obtained which describes the elongation rate of planar semiconductor nanowires growing via the vapor-liquid-solid mechanism in the substrate plane. Theoretical analysis of different regimes depending on the nanowire radius and epitaxial conditions shows that planar growth of nanowires can be limited by either the Gibbs-Thomson effect in a catalyst droplet (for small droplet size) or surface diffusion of adatoms (for larger nanowire radii. Diffusion-like dependence of the growth rate on the nanowire radius R has the form R^(-m), where the power exponent equal 1, 3/2 or 2 depending on the mechanism of surface diffusion transport.