Publications

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We report on the thermodynamic properties of binary compound mixtures of model groups II-VI semiconductors. We use the recently introduced Stillinger-Weber Hamiltonian to model binary mixtures of CdTe and CdSe. We use molecular dynamics simulations to calculate the volume and enthalpy of mixing as a function of mole fraction. The lattice parameter of the mixture closely follows Vegard's law: a linear relation. This implies that the excess volume is a cubic function of mole fraction. A connection is made with hard sphere models of mixed fcc and zincblende structures. The potential energy exhibits a positive deviation from ideal soluton behaviour; the excess enthalpy is nearly independent of temperatures studied (300 and 533 K) and is well described by a simple cubic function of the mole fraction. Using a regular solution approach (combining non-ideal behaviour for the enthalpy with ideal solution behaviour for the entropy of mixing), we arrive at the Gibbs free energy of the mixture. The Gibbs free energy results indicate that the CdTe and CdSe mixtures exhibit phase separation. The upper consolute temperature is found to be 335 K. Finally, we provide the surface energy as a function of composition. It roughly follows ideal solution theory, but with a negative deviation (negative excess surface energy). This indicates that alloying increases the stability, even for nano-particles.

Carbon nanostructures, such as nanotubes and graphene, are of considerable interest due to their unique mechanical and electrical properties. The materials exhibit extremely high strength and conductivity when defects created during synthesis are minimized. Atomistic modeling is one technique for high resolution studies of defect formation and mitigation. To enable simulations of the mechanical behavior and growth mechanisms of C nanostructures, a high-fidelity analytical bond-order potential for the C is needed. To generate inputs for developing such a potential, we performed quantum mechanical calculations of various C structures.

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Current austenitic stainless steel storage reservoirs for hydrogen isotopes (e.g. deuterium and tritium) have performance and operational life-limiting interactions (e.g. embrittlement) with H-isotopes. Aluminum alloys (e.g.AA2219), alternatively, have very low H-isotope solubilities, suggesting high resistance towards aging vulnerabilities. This report summarizes the work performed during the life of the Lab Directed Research and Development in the Nuclear Weapons investment area (165724), and provides invaluable modeling and experimental insights into the interactions of H isotopes with surfaces and bulk AlCu-alloys. The modeling work establishes and builds a multi-scale framework which includes: a density functional theory informed bond-order potential for classical molecular dynamics (MD), and subsequent use of MD simulations to inform defect level dislocation dynamics models. Furthermore, low energy ion scattering and thermal desorption spectroscopy experiments are performed to validate these models and add greater physical understanding to them.

In this project we developed t he atomistic models needed to predict how graphene grows when carbon is deposited on metal and semiconductor surfaces. We first calculated energies of many carbon configurations using first principles electronic structure calculations and then used these energies to construct an empirical bond order potentials that enable s comprehensive molecular dynamics simulation of growth. We validated our approach by comparing our predictions to experiments of graphene growth on Ir, Cu and Ge. The robustness of ou r understanding of graphene growth will enable high quality graphene to be grown on novel substrates which will expand the number of potential types of graphene electronic devices.

II-VI quantum dots, such as CdSe and CdTe, are attractive as downconversion materials for solid-state lighting, because of their narrow linewidth, tunable emission. However, for these materials to have acceptable quantum yields (QYs) requires that they be coated with a II-VI shell material whose valence band offset serves to confine the hole to the core. Confinement prevents the hole from accessing surface traps that lead to nonradiative decay of the exciton. Examples of such hole-confined core/shell QDs include CdTe/CdSe and CdSe/CdS. Unfortunately, the shell can also cause problems due to lattice mismatch, which ranges from 4-6% for systems of interest. This lattice mismatch can create significant interface energies at the heterojunction and places the core under radial compression and the shell under tangential tension. At elevated temperatures (~240°C) interfacial diffusion can relax these stresses, as can surface reconstruction, which can expose the core, creating hole traps. But such high temperatures favor the hexagonal Wurtzite structure, which has lower QY than the cubic zinc blende structure, which can be synthesized at lower temperatures, ~140°C. In the absence of alloying the core/shell structure can become metastable, or even unstable, if the shell is too thick. This can cause result in an irregular shell or even island growth. But if the shell is too thin thermallyactivated transport of the hole to surface traps can occur. In our LDRD we have developed a fundamental atomistic modeling capability, based on Stillinger-Weber and Bond-Order potentials we developed for the entire II-VI class. These pseudo-potentials have enabled us to conduct large-scale atomistic simulations that have led to the computation of phase diagrams of II-VI QDs. These phase diagrams demonstrate that at elevated temperatures the zinc blende phase of CdTe with CdSe grown on it epitaxially becomes thermodynamically unstable due to alloying. This is accompanied by a loss of hole confinement and a severe drop in the QY and emission lifetime, which is confirmed experimentally for the zinc blende core/shell QDs prepared at low temperatures. These QDs have QYs as high as 95%, which makes them very attractive for lighting. Finally, to address strain relaxation in these materials we developed a model for misfit dislocation formation that we have validated through atomistic simulations.

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TlBr is promising for g- and x- radiation detection, but suffers from rapid performance degradation under the operating external electric fields. To enable molecular dynamics (MD) studies of this degradation, we have developed a Stillinger-Weber type of TlBr interatomic potential. During this process, we have also addressed two problems of wider interests. First, the conventional Stillinger-Weber potential format is only applicable for tetrahedral structures (e.g., diamond-cubic, zinc-blende, or wurtzite). Here we have modified the analytical functions of the Stillinger-Weber potential so that it can now be used for other crystal structures. Second, past modifications of interatomic potentials cannot always be applied by a broad community because any new analytical functions of the potential would require corresponding changes in the molecular dynamics codes. Here we have developed a polymorphic potential model that simultaneously incorporates Stillinger-Weber, Tersoff, embedded-atom method, and any variations (i.e., modified functions) of these potentials. As a result, we have implemented this polymorphic model in MD code LAMMPS, and demonstrated that our TlBr potential enables stable MD simulations under external electric fields.

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We report on the strain behavior of compound mixtures of model group II-VI semiconductors. We use the Stillinger-Weber Hamiltonian that we recently introduced, specifically developed to model binary mixtures of group II- VI compounds such as CdTe and CdSe. We employ molecular dynamics simulations to examine the behavior of thin sheets of material, bilayers of CdTe and CdSe. The lattice mismatch between the two compounds leads to a strong bending of the entire sheet, with about a 0.5 to 1° deflection between neighboring planes. To analyze bilayer bending, we introduce a simple onedimensional model and use energy minimization to find the angle of deflection. The analysis is equivalent to a least-squares straight line fit. We consider the effects of bilayers which are asymmetric with respect to the thickness of the CdTe and CdSe parts. From this we learn that the bending can be subdivided into four kinds depending on the compressive/tensile nature of each outer plane of the sheet. We use this approach to directly compare our findings with experimental results on the bending of CdTe/CdSe rods. To reduce the effects of the lattice mismatch we explore diffuse interfaces, where we mix (i.e. alloy) Te and Se, and estimate the strain response.

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Elpasolite scintillators are a large family of halides which includes compounds reported to meet the NA22 program goals of <3% energy resolution at 662 keV1. This work investigated the potential to produce quality elpasolite compounds and alloys of useful sizes at reasonable cost, through systematic experimental and computational investigation of crystal structure and properties across the composition space. Discovery was accelerated by computational methods and models developed previously to efficiently identify cubic members of the elpasolite halides, and to evaluate stability of anion and cation exchange alloys.

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