<p dir="ltr">As edge computing architectures bring processing closer to data sources, there is an increasing need for memory technologies that can work effectively and consistently in a variety of situations while using minimal energy. Memristors are memory devices that have the potential to greatly increase the performance and scalability of edge devices. However, a key challenge is to achieve precise resistance switching. Silicon (Si) surfaces embedded in a proton-conducting polymer can demonstrate controllable memristor behavior wherein hydrogen (H) atoms are deposited onto the surface. When H is inside the polymer, its conductivity decreases. When H is on the silicon surface, its bulk conductivity increases due to more mid-gap traps. Migration of H atom placement can make a memristor unit cell whose impedance modulates in response to electrical signals. This study investigates the critical function of H atoms by deliberately altering their position and concentration within and upon silicon-based memristor devices. Using the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS), we investigate the impact of temperature (T) and electric field (EF) on H migration. We define a polygonal volume of Si and deposit H atoms on its top surface. After energy minimization, we apply T and EF to observe diffusion and drift of H atoms. The hopping rate depends on applied T and EF. We thus establish a relationship between the three-dimensional velocity of H and applied T and EF. We simulate several movement pathways of H atoms over time under the influence of varying T and EF acting separately or simultaneously. Therefore, we can determine the required magnitude and direction of EF and T to be introduced to the system to achieve desired H location, concentration, and configuration. Finally, we assess the device performance at different T and EF to assess memory retention rate. Our approach aims to enhance the functionality of edge computing devices and enable more effective neuromorphic computing that can emulate human brain operations. However, the limitations of this study include potential scalability issues and the necessity for precise control over hydrogen dispersion. Despite these challenges, the research provides valuable insights on how to modify the electrical characteristics of memristors, offering a way forward in the development of advanced silicon based electronic devices.</p>

SiGe 25% substrates were treated with aqueous solutions of ammonium sulfide with and without added acid to understand the adsorption of sulfur on the surface. X-ray photoelectron spectroscopy showed no sulfide layer was deposited from aqueous (NH4)(2)S alone and instead both Si and Ge oxides formed during immersion in the sulfur solution. The addition of hydrofluoric and hydrochloric acids dropped the pH from 10 to 8 and deposited sulfides, yet increased the oxide coverage on the surface and preferentially formed Ge oxides. The sulfur coverage grew with increasing concentrations of acid in the aqueous (NH4)(2)S. The simultaneous deposition of O and S is suspected to be the result of oxidized sulfur species in solution. Metal-insulator-semiconductor capacitor (MISCAP) devices were fabricated to test the electrical consequences of aqueous ammonium sulfide wet chemistries on SiGe. MISCAPs treated with acidic ammonium sulfide solutions contained fewer interface defects in the valence band region. The defect density (D-it) was on the order of 10(+12) cm(-2) eV(-1). The flat band voltage shift was lower after the acidic ammonium sulfide treatment, despite the presence of surface oxides. Adsorption of S and potentially O improved the stability of the surface and made it less electrically active. (C) 2017 American Vacuum Society.

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<div>Since the debut of graphene, many 2D materials have emerged as promising candidates for silicon alternatives to extend Moore’s Law, such as MoS₂ and phosphorene. However, some common shortcomings such as low mobility, instability and lack of massive production methods limit the exploration and applications of these materials. Here, we introduce a novel member to the 2D category – high-mobility air-stable 2D tellurium film (tellurene).</div><div><br></div><div>Tellurium (Te) is a narrow bandgap semiconductor with unique one-dimensional chiral structure. Recently, a hydrothermal synthesizing method was developed to produce large-area tellurene nanofilms with thickness ranging from tens of nanometers down to few layers. In this thesis, a thorough investigation of Te properties in 2D quantum region was first carried out by various material characterization techniques including TEM and Raman spectroscopy. Potential applications of Te-based electronics, optoelectronic and thermoelectric devices were explored, and high-performance Te FETs were achieved with record-high drive current over 1 A/mm via device scaling and contact engineering. Magneto-transport, including weak anti-localization and Shubnikov-de-Haas oscillations was studied at cryogenic temperature. Quantum Hall effect was observed for the first time in both 2D electron and hole gases with mobility of 6,000 and 3,000 cm²/Vs, and non-trivial Berry phase in Te 2D electron system was detected as the first experimental evidence of massive Weyl fermions. This work not only demonstrates the great potential of tellurene films for electronics and quantum device applications, but also expands the spectrum of topological matters into a new material species - Weyl semiconductors.</div>

<p>To sustain the upcoming paradigm shift in computations technology efficiently, innovative solutions at the lowest level of the computing hierarchy (the material and device level) are essential to delivering the required functionalities beyond what is available with current CMOS platforms. Motivated by this, in this dissertation, we explore ferroelectric-based devices for steep-slope logic and energy-efficient non-volatile-memory functionalities signifying the novel device attributes, possibilities for continual dimensional scaling with the much-needed enhancement in performance.</p> <p> </p> <p>Among various ferroelectric (FE) materials, Zr doped HfO₂ (HZO) has gained immense research attention in recent times by virtue of CMOS process compatibility and a considerable amount of ferroelectricity at room temperature. In this work, we investigate the Zr concentration-dependent crystal phase transition of Hf_1-xZ_xO₂ (HZO) and the corresponding evolution of dielectric, ferroelectric, and anti-ferroelectric characteristics. Providing the microscopic insights of strain-induced crystal phase transformations, we propose a physics-based model that shows good agreement with experimental results for 10 nm Hf_1-xZ_xO₂. Further, in a heterogeneous system, ferroelectric materials can exhibit negative capacitance (NC) behavior. Such NC effects may lead to differential amplification in local potential and can provide an enhanced charge and capacitance response for the whole system compared to their constituents. Such intriguing implications of NC phenomena have prompted the design and exploration of many ferroelectric-based electronic devices to not only achieve an improved performance but potentially also overcome some fundamental limits of standard transistors. However, the microscopic physical origin as well as the true nature of the NC effect, and direct experimental evidence remain elusive and debatable. To that end, in this work, we systematically investigate the underlying physical mechanism of the NC effect in the ferroelectric material. Based upon the fundamental physics of ferroelectric material, we investigate different assumptions, conditions, and distinct features of the quasi-static NC effect in the single-domain and multi-domain scenarios. While the quasi-static and hysteresis-free NC effect was initially propounded in the context of a single-domain scenario, we highlight that the similar effects can be observed in multi-domain FEs with soft domain-wall (DW) displacement. Furthermore, to obtain the soft-DW, the gradient energy coefficient of the FE material is required to be higher as well as the ferroelectric thickness is required to be lower than some critical values. Otherwise, the DW becomes hard, and their displacement would lead to hysteretic NC effects. In addition to the quasi-static NC, we discuss different mechanisms that can lead to the transient NC effects. Furthermore, we provide guidelines for new experiments that can potentially provide new insights on unveiling the real origin of NC phenomena.</p> <p> </p> <p>Utilizing such ferroelectric insulators at the gate stack of a transistor, ferroelectric-field-effect transistors (FeFETs) have been demonstrated to exhibit both non-volatile memory and steep-slope logic functionalities. To investigate such diverse attributes and to enable application drive optimization of FeFETs, we develop a phase-field simulation framework of FeFETs by self-consistently solving the time-dependent Ginzburg-Landau (TDGL) equation, Poisson’s equation, and non-equilibrium Green’s function (NEGF) based semiconductor charge-transport equation. Considering HZO as the FE layer, we first analyze the dependence of the multi-domain patterns on the HZO thickness (<i>T_FE</i>) and their critical role in dictating the steep-switching (both in the negative and positive capacitance regimes) and non-volatile characteristics of FeFETs. In particular, we analyze the <i>T_FE</i>-dependent formation of hard and soft domain-walls (DW). We show that, <i>T_FE</i> scaling first leads to an increase in the domain density in the hard DW-regime, followed by soft DW formation and finally polarization collapse. For hard-DWs, we describe the polarization switching mechanisms and how the domain density impacts key parameters such as coercive voltage, remanent polarization, effective permittivity and memory window. We also discuss the enhanced but positive permittivity effects in densely pattern multi-domain states in the absence of hard-DW displacement and its implication in non-hysteretic attributes of FeFETs. For soft-DWs, we present how DW-displacement can lead to effective negative capacitance in FeFETs, resulting in a steeper switching slope and superior scalability. In addition, we also develop a Preisach based circuit compatible model for FeFET (and antiferroelectric-FET) that captures the multi-domain polarization switching effects in the FE layer. </p> <p> </p> Unlike semiconductor insulators (e.g., HZO), there are ferroelectric materials that exhibit a considerably low bandgap (< 2eV) and hence, display semiconducting properties. In this regard, non-perovskite-based 2D ferroelectric -In₂Se₃ shows a bandgap of ~1.4eV and that suggests a combined ferroelectricity and semiconductivity in the same material system. As part of this work, we explore the modeling and operational principle of ferroelectric semiconductor metal junction (FeSMJ) based devices in the context of non-volatile memory (NVM) application. First, we analyze the semiconducting and ferroelectric properties of the α-In₂Se₃ van der Waals (vdW) stack via experimental characterization and first-principles simulations. Then, we develop a FeSMJ device simulation framework by self-consistently solving the Landau–Ginzburg–Devonshire equation, Poisson's equation, and charge-transport equations. Our simulation results show good agreement with the experimental characteristics of α-In₂Se₃-based FeSMJ suggesting that the FeS polarization-dependent modulation of Schottky barrier heights of FeSMJ plays a key role in providing the NVM functionality. Moreover, we show that the thickness scaling of FeS leads to a reduction in read/write voltage and an increase in distinguishability. Array-level analysis of FeSMJ NVM suggests a lower read-time and read-write energy with respect to the HfO₂-based ferroelectric insulator tunnel junction (FTJ) signifying its potential for energy-efficient and high-density NVM applications.

<p>The traditional semiconductor device scaling based on Moore’s law is reaching its physical limits. New materials hosting rich physical phenomena such as correlated electronic behavior may be essential to identify novel approaches for information processing. The tunable band structures in such systems enables the design of hardware for neuromorphic computing. Strongly correlated perovskite nickelates (ReNiO3) represent a class of quantum materials that possess exotic electronic properties such as metal-to-insulator transitions. In this thesis, detailed studies of NdNiO3 thin films from wafer-scale synthesis to structure characterization and to electronic device demonstration will be discussed.</p> <p>Atomic layer deposition (ALD) of correlated oxide thin films is essential for emerging electronic technologies and industry. We reported the scalable ALD growth of neodymium nickelate (NdNiO3) with high crystal quality using Nd(iPrCp)3, Ni(tBu2-amd)2 and ozone (O3) as precursors. By controlling various growth parameters such as precursor dose time and reactor temperature, we have optimized ALD condition for perovskite phase of NdNiO3­. We studied the structure and electrical properties of ALD NdNiO3 films epitaxially grown on LaAlO3 and confirmed their properties were comparable to those synthesized by physical vapor deposition methods. </p> <p>ReNiO3 undergoes a dramatic phase transition by hydrogen doping with catalytic electrodes independent of temperature. The electrons from hydrogen occupy Ni 3<em>d</em> orbitals and create strongly correlated insulating state with resistance changes up to eight orders of magnitudes. At room temperature, protons remain in the lattice locally near catalytic electrodes and can move by electrical fields due to its charge. The effect of high-speed voltage pulses on the migration of protons in NdNiO3 devices is discussed. After voltage pulses were applied with changing the voltage magnitude in nanosecond time scale, the resistance changes of the nickelate device were investigated. </p> <p>Reconfigurable perovskite nickelate devices were demonstrated and a single device can switch between multiple electronic functions such as neuron, synapse, resistor, and capacitor controlled by a single electrical pulse. Raman spectroscopy showed that differences in local proton distributions near the Pd electrode leads to different functions. This body of results motivates the search for novel materials where subtle compositional or structural differences can enable different gaps that can host neuromorphic functions.</p>

<p>Copper (Cu) has been used as the main conductor in interconnects due to its low resistivity. However, because of its high diffusivity, diffusion barriers/liners (tantalum nitride/tantalum; TaN/Ta) must be incorporated to surround Cu wires. Otherwise, Cu ions/atoms will drift/diffuse through the inter-metal dielectric (IMD) that separates two distinct interconnects, resulting in circuit shorting and chip failures. The scaling limit of conventional Cu diffusion barriers/liners has become the bottleneck for interconnect technology, which in turn limits the IC performance. The interconnect half-pitch size will reach ~20 nm in the coming sub-5 nm technology nodes. Meanwhile, the TaN/Ta (barrier/liner) bilayer stack has to be > 4 nm to ensure acceptable liner and diffusion barrier properties. Since TaN/Ta occupy a significant portion of the interconnect cross-section and they are much more resistive than Cu, the effective conductance of an ultra-scaled interconnect will be compromised by the thick bilayer. Therefore, two dimensional (2D) layered materials have been explored as diffusion barrier alternatives owing to their atomically thin body thicknesses. However, many of the proposed 2D barriers are prepared at too high temperatures to be compatible with the back-end-of-line (BEOL) technology. In addition, as important as the diffusion barrier properties, the liner properties of 2D materials must be evaluated, which has not yet been pursued. </p> The objective of the thesis is to develop a 2D barrier/liner that overcomes the issues mentioned. Therefore, we first visit various 2D layered materials to understand their fundamental capability as barrier candidates through theoretical calculations. Among the candidates, hexagonal-boron-nitride (h-BN) and molybdenum disulfide (MoS₂) are selected for experimental studies. In addition to studying their fundamental properties to know their potential, we have also developed techniques that can realize low-temperature-grown 2D layered materials. Metal-organic chemical vapor deposition (MOCVD) is adopted for the synthesis of BEOL-compatible MoS₂. The electrical test results demonstrate the promises of integrating 2D layered materials to the state-of-the-art interconnect technology. Furthermore, by considering not only diffusion barrier properties but also liner properties, we develop another 2D layered material, tantalum sulfide (TaS_x), using plasma-enhanced chemical vapor deposition (PECVD). The TaS_x is promising in both barrier and liner aspects and is BEOL-compatible. Therefore, we believed that the conventional TaN/Ta bilayer stack can be replaced with an ultra-thin TaS_x layer to maximize the Cu volume for ultra-scaled interconnects and improve the performance. Furthermore, Since via resistance has become the bottleneck for overall interconnect performance, we study the vertical conduction of TaS_x. Both the intrinsic and extrinsic properties of this material are investigated and engineering approaches to improve the vertical conduction are also tested. Finally, we explore the possibilities of benefiting from 2D materials in other applications and propose directions for future studies.

<div> Challenges in the semiconductor industry have resulted in the discovery of a plethora of promising materials and devices such as the III-Vs (InGaAs, GaSb, GaN/InGaN) and 2D materials (Transition-metal dichalcogenides [TMDs]) with wide-ranging applications from logic devices, optoelectronics to biomedical devices. Performance of these devices suffer significantly from scattering processes such as polar-optical phonons (POP), charged impurities and remote phonon scattering. These scattering mechanisms are long-ranged, and a quantitative description of such devices require non-local scattering calculations that are computationally expensive. Though there have been extensive studies on coherent transport in these materials, simulations are scarce with scattering and virtually non-existent with non-local scattering. </div><div> </div><div>In this work, these scattering mechanisms with full non-locality are treated rigorously within the Non-Equilibrium Green's function (NEGF) formalism. Impact of non-locality on charge transport is assessed for GaSb/InAs nanowire TFETs highlighting the underestimation of scattering with local approximations. Phonon, impurity scattering, and structural disorders lead to exponentially decaying density of states known as Urbach tails/band tails. Impact of such scattering mechanisms on the band tail is studied in detail for several bulk and confined III-V devices (GaAs, InAs, GaSb and GaN) showing good agreement with existing experimental data. A systematic study of the dependence of Urbach tails with dielectric environment (oxides, charged impurities) is performed for single and multilayered 2D TMDs (MoS2, WS2 and WSe2) providing guideline values for researchers. </div><div><br></div><div>Often, empirical local approximations (ELA) are used in the literature to capture these non-local scattering processes. A comparison against ELA highlight the need for non-local scattering. A physics-based local approximation model is developed that captures the essential physics and is computationally feasible.</div>

<div>With the transistor dimensions scaling down to a few atoms, quantum phenomena - like quantum tunneling and entanglement - will dictate the operation and performance of the next generation of electronic devices, post-CMOS era. While quantum tunneling limits the scaling of the conventional transistor, Tunneling Field Effect Transistor (TFET) employs band-to-band tunneling for the device operation. This mechanism can reduce the sub-threshold swing (S.S.) beyond the Boltzmann's limit, which is fundamentally limited to 60 mV/dec in a conventional Si-based metal-oxide-semiconductor field-effect transistor (MOSFET). A smaller S.S. ensures TFET operation at a lower supply voltage and, therefore, at lesser power compared to the conventional Si-based MOSFET.</div><div><br></div><div>However, the low transmission probability of the band-to-band tunneling mechanism limits the ON-current of a TFET. This can be improved by reducing the body thickness of the devices i.e., using 2-Dimensional (2D) materials or by utilizing heterojunction designs. In this thesis, two promising methods are proposed to increase the ON-current; one for the 2D material TFETs, and another for the III-V heterojunction TFETs.</div><div><br></div><div>Maximizing the ON-current in a 2D material TFET by determining an optimum channel thickness, using compact models, is presented. A compact model is derived from rigorous atomistic quantum transport simulations. A new doping profile is proposed for the III-V triple heterojunction TFET to achieve a high ON-current. The optimized ON-current is 325 uA/um at a supply voltage of 0.3 V. The device design is optimized by atomistic quantum transport simulations for a body thickness of 12 nm, which is experimentally feasible.</div><div> </div><div>However, increasing the device's body thickness increases the atomistic quantum transport simulation time. The simulation of a device with a body thickness of over 12 nm is computationally intensive. Therefore, approximate methods like the mode-space approach are employed to reduce the simulation time. In this thesis, the development of the mode-space approximation in modeling the triple heterojunction TFET is also documented.</div><div><br></div><div>In addition to the TFETs, quantum computing is an emerging field that utilizes quantum phenomena to facilitate information processing. An extra chapter is devoted to the electronic structure calculations of the Si:P delta-doped layer, using the empirical tight-binding method. The calculations agree with angle-resolved photoemission spectroscopy (ARPES) measurements. The Si:P delta-doped layer is extensively used as contacts in the Phosphorus donor-based quantum computing systems. Understanding its electronic structure paves the way towards the scaling of Phosphorus donor-based quantum computing devices in the future.</div>

<div> <div> <div> <p>Organic-inorganic halide perovskite solar cells have increased efficiencies substantially (from 3% to > 22%), within a few years. However, these solar cells degrade very rapidly due to humidity and no longer are capable of converting photons into electrons. Methylammonium Lead Triiodide (CH3NH3PbI3 or MAPbI3) is the most common type of halide perovskite solar cell and is the crystal studied in this thesis. Graphene is an effective encapsulation method of MAPbI3 perovskite to reduce degradation, while also being advantageous because of its excellent optical and conductive properties. Using a PMMA transfer method graphene was chemical vapor depostion (CVD) grown graphene was transferred onto MAPbI3 and reduced the MAPbI3 degradation rate by over 400%. The PMMA transfer method in this study is scalable for roll-to- roll manufacturing with fewer cracks, impurites, and folds improving upon dry transfer methods. To characterize degradation a fluorescent microscope was used to capture photoluminescence data at initial creation of the samples up to 528 hours of 80% humidity exposure. Atomic force microscopy was used to characterize topographical changes during degradation. The study proves that CVD graphene is an effective encapsulation method for reducing degradation of MAPbI3 due to humidity and retained 95.3% of its initial PL intensity after 384 hours of 80% humidity exposure. Furthermore, after 216 hours of 80% humidity exposure CVD graphene encapsulated MAPbI3 retained 80.2% of its initial number of peaks, and only saw a 35.1% increase in surface height. Comparatively, pristine MAPbI3 only retained 16% of its initial number of peaks and saw a 159% increase in surface height. </p> </div> </div> </div>