Characterization, modeling, and simulation of multiscale directed-assembly systems

Nanoscience is a rapidly developing field at the nexus of all physical sciences which holds the potential for mankind to gain a new level of control of matter over matter and energy altogether. Directed-assembly is an emerging field within nanoscience in which non-equilibrium system dynamics are controlled to produce scalable, arbitrarily complex and interconnected multi-layered structures with custom chemical, biologically or environmentally-responsive, electronic, or optical properties. We construct mathematical models and interpret data from direct-assembly experiments via application and augmentation of classical and contemporary physics, biology, and chemistry methods. Crystal growth, protein pathway mapping, LASER tweezers optical trapping, and colloid processing are areas of directed-assembly with established experimental techniques. We apply a custom set of characterization, modeling, and simulation techniques to experiments to each of these four areas. Many of these techniques can be applied across several experimental areas within directed-assembly and to systems featuring multiscale system dynamics in general. We pay special attention to mathematical methods for bridging models of system dynamics across scale regimes, as they are particularly applicable and relevant to directed-assembly. We employ massively parallel simulations, enabled by custom software, to establish underlying system dynamics and develop new device production methods

CHARACTERIZATION OF NANOSTRUCTURE, MATERIALS, AND ELECTRON EMISSION PERFORMANCE OF NEXT-GENERATION THERMIONIC SCANDATE CATHODES

Scandate cathodes, where scandia is added to the tungsten cathode pellets, have recently received substantial and renewed research interest owing to significantly improved electron emission capabilities at lower temperatures, as compared with conventional dispenser cathodes. However, there are several persistent issues including non-uniform electron emission, lack of understanding regarding scandium’s role in the emission mechanism, and unreliable reproducibility in terms of scandate cathode fabrication. As a result, scandate cathodes have not yet been widely implemented in actual vacuum electron devices (VEDs). The surface structure and chemical composition of multiple scandate cathodes – prepared with the powder using the liquid-solid (L-S) technique – and exhibiting excellent emission behavior were characterized to give insight into the fundamental mechanism(s) of operation. This was achieved with high-resolution electron microscopy techniques that include high-precision specimen lift-out. These studies showed that the micron-sized tungsten particles that compose the largest fraction of the cathode body are highly faceted and decorated with nanoscale Ba/BaO (~10 nm), as well as larger (~150 nm) Sc2O3 and BaAl2O4 particles. The experimentally identified facets were confirmed through Wulff analysis of the tungsten crystal shape and were determined to consist of {110}, {100}, and {112} facets, in increasing order of surface area prevalence. Furthermore, it is estimated that Ba atoms decorating the tungsten crystal surfaces are present in quantities such that monolayer coverage is possible at elevated temperatures. The high-resolution electron microscopy techniques used to investigate the cross section (near-surface) of the L-S scandate cathodes also revealed that the BaAl2O4 particles (100-500 nm) that attach to the larger tungsten particles are either adjacent to the smaller Sc2O3 nanoparticles or encompass them. Furthermore, high-resolution chemical analysis and 3D elemental tomography show that the two oxides always appear to be physically distinct from each other, despite their close proximity. 3D elemental tomography also showed that the Sc2O3 particles can sometimes appear inside the larger tungsten particles, but are inhomogeneously distributed. Nanobeam electron diffraction confirmed that the crystal structure of the tungsten particles are body-centered cubic, and imply that the structure remains unchanged despite the numerous complex chemical reactions that take place throughout the impregnation and activation procedures. The role of Sc and the emission mechanism for scandate cathodes are discussed. Based on characterization results and materials computation, the role of Sc in scandate cathodes is possibly related to tuning the partial pressure of oxygen in order to establish an oxygen-poor atmosphere around the cathode surface, which is a necessary condition for the formation of the (near) equilibrium tungsten shape. A thin Ba-Sc-O surface layer (~8 nm) was detected near the surface of tungsten particles, using electron energy loss spectroscopy in the scanning transmission electron microscope. This stands in stark contrast to models invoking a ~100 nm Ba-Sc-O semiconducting surface layer, which are broadly discussed in the literature. These results provide new insights into understanding the emission mechanism of scandate cathodes

Level Set Approach to Anisotropic Wet Etching of Silicon

In this paper a methodology for the three dimensional (3D) modeling and simulation of the profile evolution during anisotropic wet etching of silicon based on the level set method is presented. Etching rate anisotropy in silicon is modeled taking into account full silicon symmetry properties, by means of the interpolation technique using experimentally obtained values for the etching rates along thirteen principal and high index directions in KOH solutions. The resulting level set equations are solved using an open source implementation of the sparse field method (ITK library, developed in medical image processing community), extended for the case of non-convex Hamiltonians. Simulation results for some interesting initial 3D shapes, as well as some more practical examples illustrating anisotropic etching simulation in the presence of masks (simple square aperture mask, convex corner undercutting and convex corner compensation, formation of suspended structures) are shown also. The obtained results show that level set method can be used as an effective tool for wet etching process modeling, and that is a viable alternative to the Cellular Automata method which now prevails in the simulations of the wet etching process

Application of multi-scale computational techniques to complex materials systems

The applications of computational materials science are ever-increasing, connecting fields far beyond traditional subfields in materials science. This dissertation demonstrates the broad scope of multi-scale computational techniques by investigating multiple unrelated complex material systems, namely scandate thermionic cathodes and the metallic foam component of micrometeoroid and orbital debris (MMOD) shielding. Sc-containing scandate cathodes have been widely reported to exhibit superior properties compared to previous thermionic cathodes; however, knowledge of their precise operating mechanism remains elusive. Here, quantum mechanical calculations were utilized to map the phase space of stable, highly-faceted and chemically-complex W nanoparticles, accounting for both finite temperature and chemical environment. The precise processing conditions required to form the characteristic W nanoparticle observed experimentally were then distilled. Metallic foams, a central component of MMOD shielding, also represent a highly-complex materials system, albeit at a far higher length scale than W nanoparticles. The non-periodic, randomly-oriented constituent ligaments of metallic foams and similar materials create a significant variability in properties that is generally difficult to model. Rather than homogenizing the material such that its unique characteristic structural features are neglected, here, a stochastic modeling approach is applied that integrates complex geometric structure and utilizes continuum calculations to predict the resulting probabilistic distributions of elastic properties. Though different in many aspects, scandate cathodes and metallic foams are united by complexity that is impractical, even dangerous, to ignore and well-suited to exploration with multi-scale computational methods

Growth and Properties of Boron Phosphide Films on Silicon Carbide

Boron phosphide (BP) is a promising material for the development of high-efficiency solid-state thermal neutron detectors. However, the synthesis of good-quality BP film had been an obstacle. In this work, silicon carbide (SiC) substrates with vicinal steps instead of the conventional silicon (Si) substrates are used for BP growths. A series of growth experiments are performed and good-quality epitaxial BP films are successfully obtained and for the first time fully characterized. The optimized growth conditions are established, the film growth mechanism and defect origination mechanism are interpreted after an integrated experimental and theoretical study

Formation of Nanoclusters and Nanopillars in Nonequilibrium Surface Growth for Catalysis Applications: Growth by Diffusional Transport of Matter in Solution Synthesis

Growth of nanoclusters and nanopillars is considered in a model of surface deposition of building blocks (atoms) diffusionally transported from solution to the forming surface structure. Processes of surface restructuring are also accounted for in the model, which then yields morphologies of interest in catalysis applications. Kinetic Monte Carlo numerical approach is utilized to explore the emergence of FCC-symmetry surface features in Pt-type metal nanostructures. Available results exemplify evaluation of the fraction of the resulting active sites with desirable properties for catalysis, such as (111)-like coordination, as well as suggest optimal growth regimes

A review of wetting versus adsorption, complexions, and related phenomena: the rosetta stone of wetting

This paper reviews the fundamental concepts and the terminology of wetting. In particular, it focuses on high temperature wetting phenomena of primary interest to materials scientists. We have chosen to split this review into two sections: one related to macroscopic (continuum) definitions and the other to a microscopic (or atomistic) approach, where the role of chemistry and structure of interfaces and free surfaces on wetting phenomena are addressed. A great deal of attention has been placed on thermodynamics. This allows clarification of many important features, including the state of equilibrium between phases, the kinetics of equilibration, triple lines, hysteresis, adsorption (segregation) and the concept of complexions, intergranular films, prewetting, bulk phase transitions versus “interface transitions”, liquid versus solid wetting, and wetting versus dewetting.Seventh Framework Programme (European Commission) (Grant FP7-NMP-2009-CSA-23348-MACAN

Quantitative three-dimensional characterization of critical sizes of non-spherical TiO2 nanoparticles by using atomic force microscopy

Since both size and shape of nanoparticles are challenging to be quantitatively measured, traceable 3D measurements are nowadays an issue. 3D nanometrology plays a crucial role to reduce the uncertainty of measurements, improve traceable calibration of samples and implement new approaches, models, and methodologies in the study of the nanomaterials. AFM measurement of nanoparticles with unusual shape represent a non-trivial challenge due to the convolution with the finite size of the tip. In this work, geometric approaches for the determination of critical sizes of TiO2 anatase bipyramids and nanosheets are described. An uncertainty budget is estimated for each nanoparticle size with the aim of assessing the different sources of error to obtain a more reliable and consistent result. The combined standard uncertainties are respectively less than 5% and 10% of the dimensions of bipyramids and nanosheets. Due to the stability and monomodal distribution of their critical sizes, bipyramids and nanosheets are suitable to apply as candidate reference materials at the nanoscale. Moreover, quantitative measurements of shape and texture descriptors are discussed in order to understand the quality of the synthetized batch