Abstract
Although the vapor-liquid-solid growth of semiconductor nanowire is a non-equilibrium process, the equilibrium phase diagram of binary alloy provides important guidance on the growth conditions, such as the temperature and the equilibrium composition of the alloy. Given the small dimensions of the alloy seeds and the nanowires, the known phase diagram of bulk binary alloy cannot be expected to accurately predict the behavior of the nanowire growth. Here, we developed a unified model to describe the size- and dimensionality-dependent equilibrium phase diagram of Au-Ge binary eutectic nanoalloys based on the size-dependent cohesive energy model. It is found that the liquidus curves reduce and shift leftward with decreasing size and dimensionality. Moreover, the effects of size and dimensionality on the eutectic composition are small and negligible when both components in binary eutectic alloys have the same dimensionality. However, when two components have different dimensionality (e.g. Au nanoparticle-Ge nanowire usually used in the semiconductor nanowires growth), the eutectic composition reduces with decreasing size.
Highlights
There are some experimental and theoretical progresses in understanding how the phase diagram of alloys changes with decreasing system size[7,8,9,11,12,13,14,15,16,17,18,19]
It has been suggested that capillary effects, often represented by the Gibbs-Thomson pressure, can account for the change of phase diagram[12,16]
Since the solid solubility is so small and the solidus lines almost have a negligible effect on the VLS growth process, the solid solubility is assumed to be zero as a first-order approximation to simplify the derivation and the solidus lines will not occur in our calculated phase diagram
Summary
There are some experimental and theoretical progresses in understanding how the phase diagram of alloys changes with decreasing system size[7,8,9,11,12,13,14,15,16,17,18,19]. Adhikari et al calculated the Gibbs-Thomson modified equilibrium phase diagram of Au-Ge in the nanometer-scale regime and found that the growth-geometry eutectic temperatures were lower by 42, 22 and 11 K for nanowires with the diameter of 10, 20 and 40 nm than the corresponding bulk value[16].
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