RESUMEN
We report the findings of a systematic computational study that addresses the effects of surface segregation on the atomic distribution at equilibrium of constituent group-III atoms in freestanding ternary semiconductor In(x)Ga(1-x)As nanocrystals. Our analysis is based on density functional theory calculations in conjunction with Monte Carlo simulations of the freestanding nanocrystals using a DFT-re-parameterized valence force field description of interatomic interactions. We have determined the equilibrium concentration profiles as a function of nanocrystal size (d), composition (x), and temperature (T). The ranges of d, x, and T are explored and demonstrate surface segregation and phase separation that leads to different extents of alloying in the nanocrystal core and in the near-surface regions. We find that formation of core/shell-like quantum dots characterized by an In-deficient core and an In-rich shell with a diffuse interface is favored at equilibrium. The analysis elucidates the relationship between the constituent species distribution in the nanocrystal and the parameters that can be tuned experimentally to design synthesis routes for tailoring the properties of ternary quantum dots.
RESUMEN
Based on an atomically detailed surface growth model, we have performed kinetic Monte Carlo (KMC) simulations to determine the surface chemical composition of plasma deposited hydrogenated amorphous silicon (a-Si:H) thin films as a function of substrate temperature. Our surface growth kinetic model consists of a combination of various surface rate processes, including silyl (SiH(3)) radical chemisorption onto surface dangling bonds or insertion into Si-Si surface bonds, SiH(3) physisorption, SiH(3) surface diffusion, abstraction of surface H by SiH(3) radicals, surface hydride dissociation reactions, as well as desorption of SiH(3), SiH(4), and Si(2)H(6) species into the gas phase. Transition rates for the adsorption, surface reaction and diffusion, and desorption processes accounted for in the KMC simulations are based on first-principles density-functional-theory computations of the corresponding optimal pathways on the H-terminated Si(001)-(2x1) surface. Results are reported for two types of KMC simulations. The first employs a fully ab initio database of activation energy barriers for the surface rate processes involved and is appropriate for modeling the early stages of growth. The second uses approximate rates for all the relevant processes to account properly for the effects on the activation energetics of interactions between species adsorbed at neighboring surface sites and is appropriate to model later stages of growth toward a steady state of the surface composition. The KMC predictions for the temperature dependence of the surface concentration of SiH(x(s)) (x = 1,2,3) species, the surface hydrogen content, and the surface dangling-bond coverage are compared to experimental measurements on a-Si:H films deposited under operating conditions for which the SiH(3) radical is the dominant deposition precursor. The predictions of both KMC simulation types are consistent with the reported experimental data, which are based on in situ attenuated total reflection Fourier transformed infrared spectroscopy.
