Transmission electron microscopy (TEM) is a powerful tool for studying solidstate crystalline systems. With the advances in aberration correction, monochromation, and in situ capabilities, these microscopes are now more useful for addressing fundamental materials chemistry problems than ever before. This dissertation will illustrate the ways in which I have been using high-resolution imaging and in situ heating in the TEM during my Ph.D. research to investigate unique solid state chemistry questions. This dissertation will focus on four unique crystal systems: thermoelectric skutterudite crystals, vapor-liquid-solid (VLS) grown nanowires, and hafnium dioxide nanorods. Although these systems are very different from one another, high resolution and/or in situ heating in TEM is an integral part of each study. Through these techniques, we gain insight and knowledge of these systems that may have gone unknown through different analysis techniques. The experiments I will describe in some cases provide surprising and unexpected results that arise from the nanoscale nature of the materials and would be difficult to observe through bulk analytical methods. The work presented here helps to demonstrate the strength and versatility of TEM to address solid state chemistry questions.

In this dissertation, mesoporous silica thin films with tunable features at the nanoscale were fabricated using the triblock copolymer template pathway, with the aim of specifically harvesting the low molecular weight peptides and proteins from human serum, which has been regarded as a potential source of diagnostic biomarkers for the early detection of disease. The superior properties of mesoporous silica have been demonstrated in applications which include chemical sensing, filtration, catalysis, drug-delivery and selective biomolecular uptake. These properties depend on the architectural, physical and chemical properties of the materials, which in turn are determined by the processing parameters in evaporation-induced self-assembly (EISA). Using the different polymer templates and polymer concentration in the precursor solution, various pore size distributions, pore structures and surface hydrophilicities were obtained and applied for nanotexture-selective recovery of low mass proteins. With the assistance of mass spectrometry and statistic analysis, we demonstrated the correlation between the nanophase characteristics of the mesoporous silica thin film and the specificity and efficacy of low mass proteome harvesting. In addition, to overcome the limitations of the pre-functionalization method in polymer selection, plasma ashing was used for the first time for the treatment of the mesoporous silica surface prior to chemical modification. Opposite surface charges due to the different functional groups used, resulted in a distinctive selectivity of the low molecular weight proteins from the serum sample. The mesoporous silica chips operate with extraordinary rapidity, high reproducibility, no sample pre-processing, and substantial independence from sample acquisition and storage temperature.In conclusion our study demonstrates that the ability to tune the physicochemical properties of mesoporous silica surfaces has the potential to promote the use of this material as a tool for the selective separation and concentration of the low molecular weight proteome from complex biological fluids. / text

A better understanding of how the nanoscale environment affects the mechanical properties of materials, in particular metallic nanoparticles and nanocrystalline metals is vital to the development of next generation materials. Of special interest is obtaining a fundamental understanding of the inverse Hall-Petch Effect in nanocrystalline metals, and nanoindentation in individual nanoparticles. Understanding these subjects is critical to understanding how the mechanical properties of materials are fundamentally affected by nanoscale dimensions. These topics have been addressed by a combination of theoretical modeling and in-situ nanoindentation transmission electron microscopy (TEM) analysis. Specifically, the study of the inverse Hall-Petch effect in nanocrystalline metals will be investigated by a thorough review of the literature followed by a proposed novel theoretical model that better explains the experimentally observed behavior of nanocrystalline metals. On the other hand, the nanoindentation of individual nanoparticles is a very new research topic that has yet to aggregate a large body of experimental data. In this context, in-situ TEM nanoindentation experiments on silver nanoparticles will be first performed to determine the mechanisms of deformation in these nanostructures. A theoretical explanation for the observed deformation mechanisms will be then developed and its implications will be discussed. In addition to nanoparticles, this study will also provide unique and valuable insight into the deformation mechanisms of nanopillars, a growing area of research despite much controversy and speculation about their actual mechanisms of deformation. After studying the novel behavior of both nanocrystalline metals and nanoparticles, useful applications of both classes of materials will be explored. The discussion of applications will focus on utilizing the interesting behaviors explored in the dissertation. Of particular interest will be applications of nanoparticles and nanocrystalline materials to coatings, radiation resistance and super-plastic materials. / text

This thesis presents an analytical and experimental investigation into the capillary wicking limitation of an array of pillars. Commercial and nanopillar wicks are examined experimentally to assess the effects of micro and nanoscale capillary forces. By exerting a progressively higher heat flux on the wick, a maximum achievable mass flow was observed at the capillary limit. Through the balance of capillary and viscous forces, an ab initio analytical model is also presented to support the experimental data. Comparison of the capillary limit predicted by the analytical model and actual limit observed in experimental results are presented for three baseline wicks and two nanowicks. / text

The ability to pattern in the nanoscale to drill holes, to draw lines, to make circles, or more complicated shapes that span a few atoms in width is the main driver behind current efforts in the rapidly growing area of nanomanufacturing. In applications ranging from the microprocessor industry to biomedical science, there is a constant need to develop new tools and processes that enable the shrinking of devices. For this and more applications, nanomanufacturing using electron beams offers a window of opportunity as a top-down approach since electrons, unlike light, have a wavelength that is in the order of the atomic distance. Though the technology based on electron beams has been available for more than twenty years, new concepts are constantly being explored and developed based on fundamental approaches. As such, a tool that utilizes electron field-emission from carbon nanotubes was proposed to accomplish such feats. A full numerical analysis of electron field-emission from carbon nanotubes for nanomachining applications is presented. The different aspects that govern the process of electron field-emission from carbon nanotubes using the finite element method are analyzed. Extensive modeling is carried here to determine what the effect of different carbon nanotube geometries have on their emission profiles, what energy transport processes they are subject to, and establish what the potential experimental parameters are for nanomachining. This dissertation builds on previous efforts based on Monte Carlo simulations to determine electron deposition profiles inside metals, but takes them to next level by considering realistic emission scenarios. A hybrid numerical approach is used that combines the two-temperature model with Molecular Dynamics to study phase change and material removal in depth. The use of this method, allows the determination of the relationship between the amount of energy required to remove a given number of atoms from a metallic workpiece and the number of carbon nanotubes and their required settings in order to achieve nanomachining. Finally, the grounds for future work in this area are provided, including the need for novel electron focusing systems, as well as the extension of the hybrid numerical approach to study different materials.

Current magnetic data storage technology is encountering certain fundamental limitations that present roadblocks to its scalability to areal densities of 1 Tbit/in^2 and beyond. Next generation magnetic storage technology is expected to use optical near field techniques to heat the magnetic film locally to write data bits. This requires experimental measurement of thermal conductivity of materials with sub--100 nm resolution. This is essential for the tailoring of the thin film stack to optimize the heat transfer of the process. This can be accomplished with a simple modification to a traditional atomic force microscopy (AFM) system. The modification requires the deposition of a thin metal film on the AFM cantilever thus creating a bimetallic cantilever. The curvature of a bimetallic cantilever is sensitive to temperature. Another modification is the use of a heating laser to raise the temperature of the cantilever so that when it scans across a sample with areas of varying thermal conductivity the bimetallic deformation of the heated cantilever is altered. The resulting system is sensitive to local variations in thermal conductivity with nanoscale resolution. Nanoscale thermal conductivity measurements can then be used to optimize the heat transfer properties of the materials used in a heat assisted magnetic recording system. AFM technology can also play a key role in the development of next generation solid-state chemical sensors. An AFM can be used to measure the workfunction of a material with near atomic resolution thus enabling the study of chemical reactions with high spatial resolution. Since chemical sensors typically use a chemical reaction at their front end to monitor the prescience of a gas, an AFM system can thus be used to understand and optimize the properties of the chemical reaction by monitoring the local workfunction. In this thesis, I explain the use of atomic force microscopy in measuring thermal and chemical properties of materials with applications towards the magnetic storage industry and chemical sensing.

Compact high power fiber lasers and the vertical-external-cavity surface-emitting lasers (VECSELs) are promising candidates for high power laser sources with diffraction-limited beam quality and are currently the subject of intensive research and development. Here three large mode area fiber lasers, namely, the photonic crystal fiber (PCF) laser, the multicore fiber (MCF) laser, and the multimode interference (MMI) fiber laser, as well as the VECSEL are modeled and designed.For the PCF laser, the effective refractive index and the effective core radius of the PCF are investigated using vectorial approaches and reformulated. Then, the classical step-index fiber theory is extended to PCFs, resulting in a highly efficient vectorial effective-index method for the design and analysis of PCFs. The new approach is employed to analyze the modal properties of the PCF lasers with depressed-index cores and to effectively estimate the number of guided modes for PCFs.The MCF laser, consisting of an active MCF and a passive coreless fiber, is modeled using the vectorial mode expansion method developed in this work. The results illustrate that the mode selection in the MCF laser by the coreless fiber section is determined by the MMI effect, not the Talbot effect. Based on the MMI and self-imaging in multimode fibers, the vectorial mode expansion approach is employed to design the first MMI fiber laser demonstrated experimentally.For the design and modeling of VECSELs, the optical, thermal, and structural properties of common material systems are investigated and the most reliable material models are summarized. The nanoscale heat transport theory is applied for the first time, to the best of my knowledge, to design and model VECSELs. In addition, the most accurate strain compensation approach is selected for VECSELs incorporating strained quantum wells to maintain structural stability. The design principles for the VECSEL subcavity are elaborated and applied to design a 1040nm VECSEL subcavity that has been demonstrated for high power operation of VECSELs where near diffraction-limited output over 20 W is obtained. Physical modeling of the VECSEL is also discussed and used to compare VECSEL subcavity designs on the laser level.

The current trend towards miniaturization of modern consumer electronic devices significantly affects their design. The demand for efficient all-in-one appliances leads to smaller, yet more complex and powerful nanoelectronic devices. The increasing complexity in the design of such nanoscale Analog/Mixed-Signal Systems-on-Chip (AMS-SoCs) presents difficult challenges to designers. One promising design method used to mitigate the burden of this design effort is the use of metamodeling (surrogate) modeling techniques. Their use significantly reduces the time for computer simulation and design space exploration and optimization. This dissertation addresses several issues of metamodeling based nanoelectronic based AMS design exploration. A surrogate modeling technique which uses geostatistical based Kriging prediction methods in creating metamodels is proposed. Kriging prediction techniques take into account the correlation effects between input parameters for performance point prediction. We propose the use of Kriging to utilize this property for the accurate modeling of process variation effects of designs in the deep nanometer region. Different Kriging methods have been explored for this work such as simple and ordinary Kriging. We also propose another metamodeling technique Kriging-Bootstrapped Neural Network that combines the accuracy and process variation awareness of Kriging with artificial neural network models for ultra-fast and accurate process aware metamodeling design. The proposed methodologies combine Kriging metamodels with selected algorithms for ultra-fast layout optimization. The selected algorithms explored are: Gravitational Search Algorithm (GSA), Simulated Annealing Optimization (SAO), and Ant Colony Optimization (ACO). Experimental results demonstrate that the proposed Kriging metamodel based methodologies can perform the optimizations with minimal computational burden compared to traditional (SPICE-based) design flows.

Additive manufacturing (AM) is currently on the verge of redefining the way we produce and manufacture things. AM encompasses many technologies and subsets, which are all joint by a common denominator; they build three dimensional (3D) objects by adding materials layer-upon-layer. This family of methods can do so, whether the material is plastic, concrete, metallic or living cells which can function as organs. AM manufacturing at the micro scale introduces new capabilities for the AM family that has been proven difficult to achieve with established AM methods at the macro scale. Electrohydrodynamic jet (E-jet or EHD jet) printing is a micro AM technique which has the ability to print at high resolution and speed by exploiting physical phenomena to generate droplets using the means of an electric field. However, when printing metallic materials, this method requires nanoparticles for deposition. To obtain a stable structure the material needs to be sintered, after which the deposited material is left with a porous structure. In contrary, electrochemical methods using the well-known deposition mechanism of electroplating, can deposit dense and pure structures with the downside of slow deposition. In this thesis, a new method is proposed to micro additive manufacturing by merging an already existing technology EHD with simple electrochemistry. By doing so, we demonstrate that it is possible to print metallic structures at the micro- and nanoscale with high speeds, without the need for presynthesized nanoparticles. To achieve this, a printing setup was designed and built. Using a sacrificial wire and the solvent acetonitrile, metallic building blocks such as lines, pillars and other geometric features could be printed in copper, silver, and gold with a minimum feature size of 200 nm. A voltage dependence was found for porosity, where the densest pillars were printed at 135-150 V and the most porous at 260 V. The maximum experimental deposition speed measured up to 4.1 µm · s−1 at 220 V. Faraday’s law of electrolysis could be used to predict the experimental deposition speed at a potential of 190 V with vexp = 1.8 µm · s−1 and vtheory = 0.8 µm · s−1. The microstructure of the pillars could be improved through lowering the applied voltage. In addition, given that Faraday’s law of electrolysis could predict experimental depositions speeds well, it gives further proof to reduction being the mechanism of deposition.

<div>The rapid advance in modern electronics and photonics is pushing device design to the micro- and nano-scale, and the resulting high power density imposes immense challenges to thermal management. Promising materials like carbon nanotubes (CNTs) and graphene offer high thermal conductivity in the axial (or in-plane) directions, but their thermal transport in the radial (or cross-plane) directions are poor, limiting their applications. Hierarchical structures like pillared graphene, which is composed of many CNT-graphene junctions, have been proposed. However, thermal</div><div>interfacial resistance is a critical issue for thermal management of these systems. In this work, we have systematically explored thermal transport across interfaces,</div><div>particularly in pillared graphene and silicon/heavy-silicon.</div><div><br></div><div><div>First, by recognizing that thermal resistance of the 3D pillared graphene architecture primarily comes from CNT-graphene junctions, a simple network model of thermal transport in pillared graphene structure is developed. Using non-equilibrium molecular dynamics (NEMD), the resistance across an individual CNT-graphene junction with sp2 covalent bonds is found to be around 6 × 10−11 m2K/W, which is significantly lower than typical values reported for planar interfaces between dissimilar materials. Interestingly, when the CNT pillar length is small, the interfacial resistance</div><div>of the sp2 covalent junction is found to decrease as the CNT pillar length decreases, suggesting the presence of coherence effects. The junction resistance Rj is eventually</div><div>used in the network model to estimate the effective thermal conductivity, and the results agree well with direct MD simulation data, demonstrating the effectiveness of our model.</div></div><div><br></div><div><div>Then we identify three different mechanisms which can lead to thermal resistances across the pillared graphene junction: the material mismatch (phonon propagates from CNT to graphene), the non-planar junction (the phonon propagation direction must change), and defects (there are six heptagons at each junction). The NEMD results show that three mechanisms lead to similar resistance at the CNT-graphene junction, each at around 2.5 × 10−11 m2K/W.</div></div><div><br></div><div><div>Further, we have predicted the transmission function of individual phonon mode using the wave packet method at CNT-graphene junction. Intriguing phonon polarization conversion behavior is observed for most incident phonon modes. It is found that the polarization conversion dominates the transmission and is more significant at larger phonon wavelength. We attribute such unique phonon polarization conversion behavior to the dimensional mismatch across CNT-graphene interface. It is found that the transmission functions at the junction cannot be predicted by the conventional acoustic mismatch models due to the existence of dimensional mismatch. Further analysis shows that, the dimensionally mismatched interface, on one hand tends to reduce the transmission and conductance due to defects and the change of phonon propagation direction at the interface, while on the other hand tends to enhance the transmission and conductance due to the new phonon transport channel introduced by polarization conversion.</div></div><div><br></div><div><div>Finally, we address that many recent experiments have shown that the measured thermal boundary conductances (TBCs) significantly exceed those calculated using the Landauer approach. We identify that a key assumption that an interface is a local equilibrium system (different modes of phonons on each side of the interfaces are at the emitted phonon temperature Te), is generally invalid and can contribute to the discrepancy. We show that the measurable temperature for each individual mode is the ”modal equivalent equilibrium temperature” T rather than Te. Also,</div><div>due to the vast range of transmission functions, different phonon modes are out of local thermal equilibrium. Hence, the total conductance cannot be simply calculated as a summation of individual modal conductance. We modify the Landauer approach to include these effects and name it the ”Nonequilibrium Landauer approach”. Our approach has been used on the carbon nanotube (CNT)/graphene and Si/heavy-Si interfaces which are matched interfaces, and it gives 310% increases in TBC as compared to the conventional Landauer approach at CNT-graphene junction and even higher increase for Si/heavy-Si with small mass ratios. A convenient chart is created to estimate the conductance correction based on our approach, and it yields quite accurate results. Our work indicate that the measured high TBCs in experiments can be due to this nonequilibrium effect rather than the other proposed mechanisms, like inelastic phonon transmission and cross-interface electron-phonon coupling.</div></div><div><br></div><div><div>The results obtained in this study will provide a deeper understanding of nanoscale thermal transport across interfaces. This research also provides new perspectives of</div><div>atomic- and nano-scale engineering of materials and structures to enhance performance of thermal management.</div></div>