Graphene, an allotrope of carbon, has demonstrated exceptional mechanical, thermal, electronic, and optical properties. Complementary to such innate properties, structural modification through chemical functionalization or defect engineering can significantly enhance the properties and functionality of graphene and its derivatives. Hence, understanding structure-property relationships in graphene-based metamaterials has garnered much attention in recent years. In this thesis, we present molecular dynamics studies aimed at elucidating structure-property relationships that govern the thermomechanical response of interlayer-bonded graphene bilayers. First, we present a systematic and thorough analysis of thermal transport in interlayer-bonded twisted bilayer graphene (IB-TBG). We find that the introduction of interlayer C-C bonds in these bilayer structures causes an abrupt drop in the in-plane thermal conductivity of pristine, non-interlayer-bonded bilayer graphene, while further increase in the interlayer C-C bond density (2D diamond fraction) leads to a monotonic increase in the in-plane thermal conductivity of the resulting superstructures approaching the high in-plane thermal conductivity of 2D diamond (diamane). We also find a similar trend in the in-plane thermal conductivity of interlayer-bonded graphene bilayers with randomly distributed individual interlayer C-C bonds (RD-IBGs) as a function of interlayer C-C bond density, but with the in-plane thermal conductivity of the IB-TBG 2D diamond superstructures consistently exceeding that of RD-IBGs at a given interlayer bond density. We analyze the simulation results employing effective medium and percolation theories and explain the predicted dependence of in-plane thermal conductivity on interlayer bond density on the basis of lattice distortions induced in the bilayer structures as a result of interlayer bonding. Our findings demonstrate that the in-plane thermal conductivity of IB-TBG 2D diamond superstructures and RD-IBGs can be precisely tuned by controlling interlayer C-C bond density with important implications for the thermal management applications of interlayer-bonded few-layer graphene derivatives. Secondly, we report results on the mechanical and structural response to shear deformation of nanodiamond superstructures in interlayer-bonded twisted bilayer graphene (IB-TBG) and interlayer-bonded graphene bilayers with randomly distributed individual interlayer C-C bonds (RD-IBGs). We find that IB-TBG nanodiamond superstructures subjected to shear deformation undergo a brittle-to-ductile transition (BDT) with increasing interlayer bond density (nanodiamond fraction). However, RD-IBG bilayer sheets upon shear deformation consistently undergo brittle failure without exhibiting a BDT. We identify, explain, and characterize in atomic-level detail the different failure mechanisms of the above bilayer structures. We also report the dependence of the mechanical properties, such as shear strength, crack initiation strain, toughness, and shear modulus, of these graphene bilayer sheets on their interlayer bond density and find that these properties differ significantly between IB-TBG nanodiamond superstructures and RD-IBG sheets. Our findings show that the mechanical properties of interlayer-bonded bilayer graphene sheets, including their ductility and the type of failure they undergo under shear deformation, can be systematically tailored by controlling interlayer bond density and distribution. These findings contribute significantly to our understanding of these 2D graphene-based materials as mechanical metamaterials.

<p>Partition density functional theory (P-DFT) is a density-based embedding method used to calculate the electronic properties of molecules through self-consistent calculations on fragments. P-DFT features a unique set of fragment densities that can be used to define formal charges and local dipoles. This dissertation is concerned mainly with establishing how the optimal fragment densities and energies of P-DFT depend on the specific methods employed during the self-consistent fragment calculations. First, we develop a procedure to perform P-DFT calculations on three-dimensional heteronuclear diatomic molecules, and we compare and contrast two different approaches to deal with non-integer electron numbers: Fractionally occupied orbitals (FOO) and ensemble averages (ENS). We find that, although both ENS and FOO methods lead to the same total energy and density, the ENS fragment densities are less distorted than those of FOO when compared to their isolated counterparts. Second, we formulate partition spin density functional theory (P-SDFT) and perform numerical calculations on closed- and open-shell diatomic molecules. We find that, for closed-shell molecules, while P-SDFT and P-DFT are equivalent for FOO, they partition the same total density of a molecule differently for ENS. For open-shell molecules, P-SDFT and P-DFT yield different sets of fragment densities for both FOO and ENS. Finally, by considering a one-electron system, we investigate the self-interaction error (SIE) produced by approximate exchange-correlation functionals and find that the molecular SIE can be attributed mainly to the non-additive Hartree-exchange-correlation energy.</p>

<p>Developing a hybrid platform that combines nanophotonic circuits and atomic physic may provide new chip-scale devices for quantum application or versatile tools for exploring photon-mediated long-range quantum systems. However, this challenging project demands the excellent integration of cold atom trapping and manipulation technology with cutting-edge nanophotonics circuit design and fabrication. In this thesis project, we aim to develop a novel suspended membrane platform that serves as a quantum interface between laser-cooled, trapped atoms in an ultrahigh vacuum and the photons guided in the nanophotonic circuits based on high-quality silicon nitride microring resonators fabricated on a transparent membrane substrate. </p> <p><br></p> <p>The proposed platform meets the stringent performance requirements imposed by nanofabrication and optical physics in an ultra-high vacuum. These include a high yield rate for mm-scale suspended dielectric photonic devices, minimization of the surface roughness to achieve ultrahigh-optical quality, complete control of optical loss/in-coupling rate to achieve critical photon coupling to a microring resonator, and high-efficiency waveguide optical input/output coupler in an ultrahigh vacuum environment. This platform is compatible with laser-cooled and trapped cold atoms. The experimental demonstration of trapping and imaging single atoms on a photonic resonator circuit using optical tweezers has been demonstrated. Our circuit design can potentially reach a record-high cooperativity parameter C$>$500 for single atom-photon coupling, which is of high importance in realizing a coherent quantum nonlinear optical platform and holds great promise as an on-chip atom-cavity QED platform.</p>

Previous research in InGaN/GaN light emitting diodes (LEDs) employing semi-classical drift-diffusion models has used reduced polarization constants without much physical explanantion. This paper investigates possible physical explanations for this effective polarization reduction in InGaN LEDs through the use of the simulation software SiLENSe. One major problem of current LED simulations is the assumption of perfectly discrete transitions between the quantum well (QW) and blocking layers when experiments have shown this to not be the case. The In concentration profile within InGaN multiple quantum well (MQW) devices shows much smoother and delayed transitions indicative of indium diffusion and drift during common atomic deposition techniques (e.g. molecular beam epitaxy, chemical vapor deposition). In this case the InGaN square QW approximation may not be valid in modeling the devices' true electronic behavior. A simulation of a 3QW InGaN/GaN LED heterostructure with an AlGaN electron blocking layer is discussed in this paper. Polarization coefficients were reduced to 70% and 40% empirical values to simulate polarization shielding effects. QW shapes of square (3 nm), trapezoidal, and triangular profiles were used to simulate realistic QW shapes. The J-V characteristic and electron-hole wavefunctions of each device were monitored. Polarization reduction decreased the onset voltage from 4.0 V to 3.0 V while QW size reduction decreased the onset voltage from 4.0 V to 3.5 V. The increased current density in both cases can be attributed to increased wavefunction overlap in the QWs.

Photodetectors are a kind of semiconductor devices that convert incoming light to an electrical signal. Photodetectors are classified based on their different structure, fabrication technology, applications and different sensitivity. Infrared photodetectors are widely used in many applications such as night vision, thermal cameras, remote temperature sensing, and medical diagnosis etc.   All detectors have material inside that is sensitive to incoming light. It will absorb the photons and, if the incoming photons have enough energy, electrons will be excited to higher energy levels and if these electrons are free to move, under the effect of an external electric field, a photocurrent is generated.   In this project Fourier Transform Infrared (FT-IR) Spectroscopy is used to investigate a new kind of photodiodes that are based on self-assembled semiconductor nanowires (NWs) which are grown directly on the substrate without any epi-layer. The spectrally resolved photocurrent (at different applied biases) and IV curves (in darkness and illumination) for different temperatures have been studied respectively. Polarization effects (at low and high Temperatures) have been investigated.  The experiments are conducted for different samples with high concentration of NWs as well as with lower concentration of NWs in the temperature range from 78 K (-195ºC) to 300 (27ºC). These photodiodes are designed to work in near infrared (NIR) spectral range.   The results show that the NW photodetectors indeed are promising devices with fairly high break down voltage, change of photocurrent spectra with polarized light, low and constant reverse saturation current (Is). The impact of different polarized light on photocurrent spectra has been investigated and an attempt has been made to clarify the observed double peak of InP photocurrent spectrum. Our investigations also include a comparison to a conventional planar InP p-i-n photodetector.

The processors and digital circuits designed today contain billions of transistors on a small piece of silicon. As devices are becoming smaller, slimmer, faster, and more efficient, the transistors also have to keep up with the demands and needs of the daily user. Unfortunately, the CMOS technology has reached its limit and cannot be used to scale down due to the transistor's breakdown caused by short channel effects. An alternative solution to this is the FinFET transistor technology, where the gate of the transistor is a three dimensional fin that surrounds the transistor and prevents the breakdown caused by scaling and short channel effects. FinFET devices are reported to have excellent control over short channel effects, high On/Off Ratio, extremely low gate leakage current and relative immunization over gate edge line roughness. Sub 20 nm node size is perceived to be the limit of scaling the CMOS transistors, but FinFETs can be scaled down further because of its unique design. Due to these advantages, the VLSI industry has now shifted to FinFET in implementation of their designs. However, these transistors have not been completely opened to academia. Analyzing and observing the effects of these devices can be pivotal in gaining an in-depth understanding of them. This thesis explores the implementation of FinFETs using a standard cell library designed using these transistors. The FinFET package file used to design these cells is a 15nm FinFET technology file developed by NCSU in collaboration with Cadence and Mentor Graphics. Post design, the cells were characterized, the results were analyzed and compared with cells designed using CMOS transistors at different node sizes to understand and extrapolate conclusions on FinFET devices.

<p>This dissertation discusses the theoretical methods for quantum scattering in the context of x-ray scattering from electrons and classical scattering in the context of collisions between Rydberg atoms.</p> <p><br></p> <p>A method for describing non-relativistic x-ray scattering from bound electrons is presented. The approach described incorporates the full spatial dependence of the incident x-ray field and is non-perturbative in the incident x-ray field. The x-ray scattering probability obtained by numerical solution for the case of free-electrons is bench-marked with well known analytical free-electron results.</p> <p><br></p> <p>A recent investigation by Fuchs \emph{et al.} [Nat. Phys. 11, 964 (2015)] revealed an anomalous frequency shift of at least 800 eV in non-linear Compton scattering of high-intensity x-rays by electrons in solid beryllium. The x-ray scattering approach described is used to explore the role of binding energy, band structure, electron-electron correlation and a semi-Compton channel in the frequency shift of scattered x-rays for different scattered angles. The results of the calculation do not exhibit an additional redshift for the scattered x-rays beyond the non-linear Compton shift predicted by the free-electron model. </p> <p><br></p> <p>The interference between Compton scattering and nonlinear Compton scattering from a two-color field in the x-ray regime is theoretically analyzed for bound electrons. A discussion of the underlying phase shifts and the dependence of the interference effect on the polarizations of the incident and outgoing fields are presented. </p> <p><br></p> <p>The problem of using x-ray scattering to image the dynamics of an electron in a bound system is examined. Previous work on imaging electronic wave-packet dynamics with x-ray scattering revealed that the scattering patterns deviate substantially from the notion of instantaneous momentum density of the wave packet. Here we show that the scattering patterns can provide clear insights into the electronic wave packet dynamics if the final state of the scattered electron and the scattered photon momentum are determined simultaneously. The scattering probability is shown to be proportional to the modulus square of the Fourier transform of the instantaneous electronic spatial wave function weighted by the final state of the electron.</p> <p><br></p> <p>Collisional ionization between Rydberg atoms is examined. The dependence of the ionization cross section on the magnitude and the direction of orbital angular momentum of the electrons and the direction of the Laplace-Runge-Lenz vector of the electrons is studied. The case of exchange ionization is examined and its dependence on the magnitude of angular momentum of the electrons is discussed.</p> <p><br></p>

Optical scattering techniques are suitable probes for studying weak disordered refractive index media such as biological cells and tissues. Several brain diseases accompany the nano-to-submicron scales’ structural alterations of the basic building blocks of cells/tissues in the brain and skin fibroblasts. For example, several molecular modifications such as DNA methylation, and histone degradation occur in cells earlier than morphological changes detectable at a microscopic level. These alterations also change the refractive index structures of the cells/tissues at the nano-to-submicron scales. Unfortunately, traditional methods do not allow the detection of these alterations in the early stages of diseases. Recent developments in mesoscopic optical physics-based techniques can probe these alterations. Particularly, mesoscopic light transport and localization approaches enable the measurements and quantifications of the degree of structural alterations in the cells/tissues and unprecedented information on progressive brain diseases. This dissertation provides a detailed study of the structural changes at nano-to-submicron levels in human brain cells/tissues and human skin fibroblasts in two major neurodegenerative diseases, Alzheimer’s disease (AD) and Parkinson's disease (PD), using dual spectroscopic imaging techniques, namely partial wave spectroscopy (PWS) for light transport and inverse participation ratio (IPR) for weak light localization. In particular, a nanoscale-sensitive advanced PWS technique is used to quantify the structural alterations in cells/tissues. Further, the IPR technique is used to quantify molecular-specific mass density alterations within cells using their light localization properties via confocal imaging. These dual optical scattering techniques were utilized to measure the degree of structural disorders, termed ‘disorder strength’, by distinguishing the diseased cells/tissues from normal ones in the human brain and human skin fibroblasts due to neurodegenerative diseases. Our results show that the degree of structural disorder (����) increases in the affected cells and tissues relative to the normal, both at the cellular/tissue level and in the DNA molecular mass density structural levels. The results of the studies strongly reveal that the degree of structural disorder strength (����) is an effective biomarker/numerical indicator for brain disease diagnostics.

The widespread pollution of mercury motivates research into its atmospheric chemistry and transport. Gaseous elemental mercury (Hg(0)) dominates mercury emission to the atmosphere, but the rate of its oxidation to mercury compound (Hg(II)) plays a significant role in controlling where and when mercury deposits to ecosystems. Atomic bromine is regarded as the main oxidant for Hg(0) oxidation, known to initiate the oxidation via a two-step process in the atmosphere – formation of BrHg (R1) and subsequent reactions of BrHg with abundant free radicals Y, i.e., NO2, HOO, etc. (R2), where the reaction of BrHg +Y could also lead to the reduction of Hg(I) to Hg(0) (R3). A different oxidation pathway of BrHg + O3 (R4) is currently regarded as the dominant Hg(II) oxidation pathway in the atmosphere. Hg + Br + M → BrHg + M (R1) BrHg + Y + M → BrHgY + M (R2) BrHg + Y → BrY +Hg (R3) BrHg + O3 → BrHgO + O2 (R4) While the rate constants of R1 have been experimentally measured a decade ago, this research focuses on the experimental kinetic studies on the reaction of R2-R4 to better assist the efforts to predict how emission reductions impact the spatial distribution of mercury entry into ecosystems. The kinetic studies of BrHg redox chemistry are conducted by utilizing laser photolysis-laser induced fluorescence-cavity ringdown spectroscopy (LP-LIF-CRDS) systems, where BrHg radicals are generated via laser photolysis and monitored in the reaction via LIF and CRDS measurements. We report mainly on our experimental kinetic studies of the redox reactions of BrHg with relatively abundant trace gases such as NO2, NO, O3, O2, and VOCs, especially on the temperature and pressure dependence of the reaction rate constants using our LP-LIF system. We present the development and the characterization of a novel LP-CRDS system, which is a powerful tool to study reactions during which fluorescence quenching interferes with LIF measurement, and to study the spectroscopy of Hg(I) and Hg(II) compounds.

<p>Dipole-dipole interactions are ubiquitous fundamental physical phenomena that govern physical effects such as Casimir Forces, van der Waals forces, collective Lamb shifts, cooperative decay, and resonance energy transfer. These interactions are associated with real and virtual photon exchange between the interacting emitters. Such interactions are crucial in realizing quantum memories, novel super-radiant light sources, and light-harvesting devices. Owing to this, the control and modification of dipole-dipole interactions have been a longstanding theme. The electromagnetic environment plays a crucial role in enhancing the range and strength of the interactions. This work focuses on modifying the nanophotonic environment near interacting emitters to enhance dipole-dipole interactions instead of spontaneous emission. To this end, we focus on engineering the nanophotonic environment to enhance the strength and range of dipole-dipole interactions between an ensemble of emitters. We explore ordered and disordered nanophotonic structures. We experimentally demonstrate long-range dipole-dipole interactions mediated by surface lattice resonances in a periodic plasmonic nanoparticle lattice. Further, the modified electromagnetic environment reduces the apparent dimensionality of the interacting system compared to non-resonant in-homogeneous and homogeneous environments. We also develop a spectral domain inverse design technique for the accelerated discovery of disordered metamaterials with unique spectral features. </p> <p>Further, we explore the novel regimes of light localization at near-zero-index in such disordered media. The disordered near-zero-index medium reveals enhanced localization and near-field chirality. This work paves the way to engineer the electromagnetic nanophotonic environment to realize enhanced long-range dipole-dipole interactions.</p>