<p>Since the discovery of graphene, two-dimensional (2D) materials have attracted broad interests for transistor applications due to their atomically thin nature. This thesis studies nano-transistors based on 2D materials for several novel applications, including tunneling transistors for low-power electronics and reconfigurable transistors for hardware security.</p><p>The first part of the thesis focuses on tunneling field-effect transistors (TFETs). Since the current injection in a conventional MOSFET depends on thermionic injection over a gate-controlled barrier, the subthreshold swing (SS) of MOSFET is fundamentally limited to 60 mV/dec at room temperature, hindering the supply voltage scaling of integrated circuits (ICs). Utilizing band-to-band tunneling (BTBT) as current injection mechanism, TFETs overcome the SS limit by filtering out the Fermi tail in the source and achieve steep-slope switching. However, existing demonstrations of TFETs are plagued by low on-currents and degraded SS, largely due to the large tunneling distances caused by non-scaled body thicknesses, making 2D materials a promising candidate as channel materials for TFETs. In this thesis, we demonstrate a prototype TFET based on black phosphorus (BP) adopting electrostatic doping that is tuned by multiple top-gates, which allows the device to be reconfigured into multiple operation modes. The band-to-band tunneling mechanism is further confirmed by source-doping-dependent and temperature-dependent measurements, and the performance improvement of BP TFETs with further body and oxide thicknesses scaling is projected by atomistic simulation. In addition, a vertical BP TFET with a large tunneling area is also demonstrated, and negative differential resistance (NDR) is observed in the device.</p><p>The second part of the thesis focuses on reconfigurable nano-transistors with tunable p- and n-type operations and the implementation of hardware security based on such transistors. Polymorphic gate has been proposed as a hardware security primitive to protect the intellectual property of ICs from reverse engineering, and its operation requires transistors that can be reconfigured between p-type and n-type. However, a traditional CMOS transistor relies on substitutional doping, and thus its polarity cannot be altered after the fabrication. By contrast, 2D nano-transistors can attain both electron and hole injections. In this thesis, we review the Schottky-barrier injection in 2D transistors and demonstrate the feasibility of achieving complementary p-type and n-type transistors using BP as channel material by adopting metal contacts with different work functions. In this design, however, the discrepancy in the p-FET and n-FET device structures makes it unsuitable for reconfigurable transistors. Therefore, we continue to modify the device design to enable reconfigurable p-type and n-type operations in the same BP transistor. Finally, a NAND/NOR polymorphic gate is experimentally demonstrated based on the reconfigurable BP transistors, showing the feasibility of using 2D materials to enable hardware security.</p><p>In the last part, we demonstrate an artificial sub-60 mV/dec switching in a metal-insulator-metal-insulator-semiconductor (MIMIS) transistor. Negative capacitance FETs (NC-FETs) have attracted wide interest as promising candidates for steep-slope devices. However, the detailed mechanisms of the observed steep-slope switching are under intense debate. We show that sub-60 mV/dec switching can be observed in a WS2 transistor with an MIMIS structure – without any ferroelectric component. Using a resistor-capacitor (RC) network model, we show that the observed steep-slope switching can be attributed to the internal gate voltage response to the chosen varying gate voltage scan rates. Our results indicate that the measurement-related artefacts can lead to observation of sub-60 mV/dec switching and that experimentalists need to critically assess their measurement setups.</p>

Since their discovery at the beginning of the 21st century, two-dimensional (2D) materials have emerged as one of the most exciting material groups offering unique properties which promise a plethora of potential applications in nanoelectronics, quantum computing, and surface science. The progress in the study of 2D materials has advanced rapidly stimulated by the ever-growing interest in their behavior and the fact that they are the ideal specimen for transmission electron microscopy (TEM), as their geometry allows to identify every single atom. Their morphology – 2D materials consist of “surface” only – at the same time makes them sensitive to beam damage, since high-energy electrons easily sputter atoms and introduce defects. While this is in general not desirable – as non-destructive imaging is aimed at – it allows to precisely quantify the damage in TEM and even pattern the 2D material with atomic resolution using the electron beam. Alternatively, patterning of 2D materials can be achieved using focused ion irradiation, which makes studying its effect on 2D materials relevant and essential. In this thesis, we theoretically study the effects of electron and ion irradiation on 2D materials, exemplarily on 2D MoS2 . Specifically, we address the combined effect of electronic excitations and direct momentum transfer by high-energy electrons (knock-on damage) in 2D MoS2 using advanced first-principles simulation techniques, such as Ehrenfest dynamics based on time-dependent density functional theory (DFT). Here, we stress the importance of the combined effect of ionization damage and knock-on damage as neither of these alone can account for experimentally-observed defect production below the displacement threshold – the minimum energy required for the displacement of an atom from the pristine system. A mechanism of defect production relying on the localization of the electronic excitation at the emerging vacancy site is presented. The localized excitation eventually leads to a significant drop in the displacement threshold. The combination of electronic excitation and knock-on damage may in addition to beam-induced chemical etching explain the observed sub-threshold damage in low voltage TEM experiments. Apart from non-destructive imaging, electrons may be used to modify the 2D material intentionally. In this light, we consider the electron-beam driven phase transformation in 2D MoS2 , where the semiconducting polymorph transforms into its metallic counterpart. The phase energetics and a possible transformation mechanism under electron irradiation are investigated using DFT based first-principles calculations. The detailed understanding of the interaction of the electron beam with the 2D material promises to improve the patterning resolution enabling circuit design on the nanoscale. Ion irradiation employed in focussed ion beams (FIB), e.g., the helium ion microscope (HIM) constitutes another tool widely used to pattern and even image 2D materials. Ion bombardment experiment usually carried out for the 2D material placed on a substrate are frequently rationalized using simulations for free-standing systems neglecting the effect of the substrate. Combining Monte Carlo with analytical potential molecular dynamics simulations, we demonstrate that the substrate plays a crucial role in damage production under ion irradiation and cannot be neglected. Especially for light ions such as He and Ne, which are usually used in the HIM, the effect of the substrate needs to be considered to account for the increased number of defects and their broadened spatial distribution which limits the patterning resolution for typical HIM energies. / Seit ihrer Entdeckung Anfang des 21. Jahrhunderts haben sich zwei-dimensionale (2D) Materialien zu einer der spannendsten Materialklassen im Forschungsfeld aus Materialwissenschaft, Physik und Chemie entwickelt. Ihre einzigartigen Eigenschaften versprechen eine Vielzahl potentieller Anwendungen in der Nanoelektronik, für Quantencomputer und in der Oberflächenwissenschaft. Beflügelt durch das wachsende Interesse an ihrem Verhalten und der Tatsache, dass sie die idealen Proben für die Transmissions-Elektronen-Mikroskopie (TEM) darstellen – ihre Geometrie erlaubt es, jedes einzelne Atom zu identifizieren – sind die Forschungen an 2D-Materialien rapide vorangeschritten. Ihre Morphologie – 2D-Materialien bestehen nur aus “Oberfläche” – bedingt zugleich ihre Sensitivität bezüglich Strahlschäden. Hochenergetische Elektronen lösen sehr leicht Atome aus dem 2D-Material und induzieren Defekte. Obwohl dies im Allgemeinen unerwünscht ist – Ziel ist eine nicht-destruktive Bildgebung – erlaubt es doch präzise Einblicke in die Schadensentstehung im TEM. Überdies können 2D-Materialien mit Hilfe des Elektronenstrahls mit atomarer Auflösung strukturiert werden. Alternativ kann die Strukturierung des 2D-Materials über fokussierte Ionenstrahlung erfolgen, weshalb es lohnenswert erscheint, auch deren Effekt auf 2D-Materialien zu untersuchen. In dieser Arbeit werden die Effekte von Elektronen- und Ionenstrahlung auf 2D-Materialien aus theoretischer Sicht exemplarisch an 2D-MoS2 untersucht. Besonderes Augenmerk liegt dabei auf dem kombinierten Effekt von elektronischer Anregung und dem direkten Impulsübertrag durch hochenergetische Elektronen (Kollisionsschaden) in 2D-MoS2 , der durch die Anwendung von Ab-Initio-Simulationstechniken wie der Ehrenfest-Molekulardynamik, basierend auf zeitabhängiger Dichtefunktionaltheorie (DFT), studiert wird. Dabei liegt die Betonung auf der Kombination beider Effekte, da weder Ionisierungs- noch Kollisionsschäden allein die experimentell beobachtete Defekterzeugung unterhalb der Displacement Threshold – der notwendigen Mindestenergie, um ein Atom aus dem reinen Material herauszulösen – erklären. Ein möglicher Mechanismus der Defekterzeugung, basierend auf der Lokalisierung der elektronischen Anregung an der entstehenden Vakanzstelle, wird vorgeschlagen. Die lokalisierte Anregung führt dabei schließlich zu einem signifikanten Absinken der Displacement Threshold. Die Kombination von elektronischer Anregung und Kollisionsschaden trägt neben strahlinduzierten chemischen Reaktionen zur Erklärung der beobachteten Schäden unterhalb der Displacement Threshold in Niederspannungs-TEM-Experimenten bei. Neben nicht-destruktiver Bildgebung können Elektronenstrahlen auch dafür benutzt werden, 2D-Materialien gezielt zu modifizieren. In diesem Sinne wird der elektronenstrahl-induzierte Phasenübergang in 2D-MoS2 , bei dem sich das Material von einem halbleitenden in einen metallischen Zustand transformiert, betrachtet. Die Phasenenergetik und ein möglicher Transformationsmechanismus werden unter Zuhilfenahme von DFT-basierten Ab-Initio-Simulationen untersucht. Das detaillierte Verständnis der Interaktion des Elektronenstrahls mit dem 2D-Material verspricht dabei die Strukturierungsauflösung zu verbessern und ermöglicht Schaltkreisdesign auf der Nanoskala. Fokussierte Ionenstrahlen, wie sie in Ionenstrahlinstrumenten – wie dem Helium-Ionen-Mikroskop (HIM) zum Einsatz kommen – stellen ein weiteres häufig verwendetes Werkzeug zur Modifikation sowie zur Bildgebung von 2D-Materialien dar. Ionenstrahlexperimente – üblicherweise mit dem auf einem Substrat platzierten 2D-Material durchgeführt – werden hingegen oft mit Simulationen für freistehende 2D-Materialien rationalisiert, wobei jegliche Einwirkung des Substrats vernachlässigt wird. Die Kombination von Monte-Carlo-Simulationen mit Molekulardynamik-Simulationen (auf der Basis analytischer Potentiale) in dieser Arbeit verdeutlicht, dass das Substrat eine wichtige Rolle in der Defekterzeugung spielt und nicht vernachlässigt werden kann. Besonders für leichte Ionen, wie He und Ne, wie sie typischerweise im HIM zum Einsatz kommen, sollte der Effekt des Substrats berücksichtigt werden. Dieses führt für typische Ionenenergien im HIM – im Vergleich zum freistehenden 2D-Material – zu einer ansteigenden Anzahl an Defekten und einer breiteren räumlichen Defektverteilung, welche die Strukturierungsauflösung begrenzt.

Detta projekts mål har varit att undersöka tre olika 2D-materials triboelektriska egenskaper och därmed placera dem i en triboelektrisk serie. Detta utfördes genom att använda en triboelektrisk nanogenerator (TENG) och mäta den resulterande spänningen. Tio stycken motmaterial applicerades mot varje 2D-material på nanogeneratorn. Utifrån resultatet var det möjligt uppmärka typiska vågformer för en TENG, alltså kunde resultatet från mätningen antas vara från den triboelektriska effekten. 2D-materialen placerades tillsammans med dess motmaterial i en triboelektrisk serie och sorterades sedan för att bestämma dess elektronaffinitet. För de tre 2D-materialen hade de gemensamt att ETFE och FEP tillhör den positiva sidan av den triboelektriska serien relativt de 2D-materialen. Resten, alltså: cellofan, kapton, LDPE, nylon, PEEK, PEI, polypropylene och PTFE, placerades negativt i deras respektives 2D-materials serie. Dock blev resultatet ej som förväntat, då ordningen på motmaterialen i serien kunde antas vara samma för alla 2D-material, men detta var inte vad som hittades. Anledningen till detta kan möjligtvis vara ytladdningar som kan ha överförts till materialen medans de hanterades, eller på grund av ytstrukturen av 2D-materialen. Därför föreslås att detta arbete kan förbättras genom mer varsam hantering och spridning av materialen över dess plattform.

No description available.

Oxide ultra-thin film surfaces have properties and structures that are significantly different from the terminations of the corresponding bulk crystals. For example, surface structures of epitaxial ultra-thin oxide films are highly influenced by the crystallinity and electronegativity of the metal substrates they grown on. Some enhanced properties of the novel reconstructions are related to catalysis, sensing and microelectronics, which has resulted in an increasing interest in this field. Ultra-thin TiO_x films were grown on Au(111) substrates in this work. Two well-ordered structures within monolayer coverage - honeycomb (HC) and pinwheel - were generated and investigated. Special attention has been paid to the uniform (2 x 2) Ti₂O₃ HC phase including its regular structure and imperfections such as domain boundaries (DBs) and point defects. Linear DBs with long-range repeating units have been observed; density functional theory (DFT) modelling has been used to simulate their atomic structures and calculate their formation energies. Rotational DBs/defects show up less frequently, however a six-fold symmetrical 'snowflake' DB loop stands out. Two types of point defects have been discovered and assigned to Ti vacancies and oxygen vacancies/hydroxyl groups. Their diffusion manners and pairing habits have been discussed within an experimental context. The results of growing NbO_x ultra-thin films on Au(111) are also presented in this thesis. An identical looking (2 x 2) HC structure to the Ti₂O₃ ultra-thin film has been formed; a stoichiometry of Nb2O3 is suggested. Another interesting reconstruction is a hollow triangle structure. Various sizes have been found, and sides of these equilateral triangles all show a double-line feature aligned along the { 1 ₁⁻ } directions of the Au(111) lattice. Chemical composition characterisations of NbO_x thin films are still required as is DFT modelling. Experimental techniques used in this thesis include scanning tunnelling microscopy (STM), low energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). Ultra-thin oxide films were created by physical vapour deposition (PVD) in ultra-high vacuum (UHV) systems.

[pt] O dissulfeto de molibdênio bidimensional (MoS2 2D) tem atraído significativa atenção devido às suas propriedades eletrônicas e ópticas únicas, tornando-se um material promissor para diversas aplicações, como dispositivos optoeletrônicos e sistemas de armazenamento de energia. Esta tese investiga métodos para aprimorar a emissão de fotoluminescência (PL) de MoS2 monocamada por meio de diferentes tratamentos. Os experimentos realizados visaram criar defeitos na estrutura cristalina de forma controlada, atacando o MoS2 2D com íons. As amostras foram obtidas via Deposição Química a Vapor (CVD). As alterações morfológicas e características eletro-ópticas foram avaliadas por Microscopia de Força Atômica (AFM), Espectroscopia Raman Ressonante e Espectroscopia de Fotoluminescência (PL). A primeira rodada de experimentos utilizou um tratamento de Plasma de Nitrogênio. Evidências de AFM da integridade da morfologia são apresentadas, embora o sinal de PL tenha sido significativamente atenuado para os parâmetros utilizados. A Espectroscopia Raman mostra uma evolução de características-chave à medida que defeitos são progressivamente criados, a saber, a Largura a Meia Altura (FWHM) dos modos vibracionais de segunda ordem 2LA(K) e 2LA(M). Posteriormente, um tratamento com feixes de íons de Hélio foi aplicado, levando a resultados positivos ao controlar o tempo e a energia do tratamento. Os espectros de emissão de fotoluminescência revelam que a intensidade do sinal foi aumentada em até duas vezes. Medidas de Raman Ressonante indicaram que a criação de defeitos foi controlada (com características de segunda ordem praticamente inalteradas). A análise de AFM demonstrou que não houve mudança da escala micrométrica devido aos tratamentos. Este tratamento constitui um método fácil para aprimorar a emissão de fotoluminescência de amostras de MoS2 monocamada crescidas via CVD para futuras aplicações em dispositivos. / [en] Two-dimensional molybdenum disulfide (2D MoS2) has gained significant attention due to its unique electronic and optical properties, making it a promising material for various applications, such as optoelectronic devices and energy storage systems. This thesis investigates methods to enhance the photoluminescence (PL) emission of monolayer MoS2 through different treatments. The experiments performed aimed to achieve this by creating defects on the crystal structure in a controlled manner, attacking the 2D MoS2 with ions. The samples were obtained via Chemical Vapor Deposition (CVD). The changes in morphology and electro-optical features were assessed via Atomic Force Microscopy (AFM), Resonant Raman Spectroscopy, and Photoluminescence (PL) Spectroscopy. The first round of experiments employed a Nitrogen Plasma treatment. AFM evidence of the integrity of the morphology is presented, although the PL signal was significantly quenched for the parameters used. Raman Spectroscopy shows an evolution of key features as defects are progressively created, namely the second-order 2LA(K) and 2LA(M) vibrational modes Full Width at Half Maximum (FWHM). Afterwards, a Helium ion beam treatment was applied, yielding positive results when controlling treatment time and energy. Photoluminescence emission spectra revealed the signal intensity was enhanced by up to a factor of 2. Resonant Raman measurements indicated a controlled defect creation was achieved (with practically unchanged second-order features). AFM analysis demonstrated no change in the micrometer scale dut to the treatments. This treatment constitutes a facile method for enhancing CVD grown monolayer MoS2 samples PL emission for future device applications.

<div>The work involves two new method implementation and application in the Quantum transport community for nano-scale electronic devices. </div><div><br></div><div>First method: Ab-initio Tight-Binding(TB)</div><div> </div><div>As the surfacing of novel 2D materials, layers can be stacked freely on top of each other bound by Van der Waals force with atomic precision. New devices created with unique characteristics will need the theoretical guidance. The empirical tight-binding method is known to have difficulty accurately representing Hamiltonian of the 2D materials. Maximally localized Wannier function(MLWF) constructed directly from ab-initio calculation is an efficient and accurate method for basis construction. Together with NEGF, device calculation can be conducted. The implementation of MLWF in NEMO5 and the application on 2D MOS structure to demystify interlayer coupling are addressed. </div><div> </div><div>Second method: Büttiker-probe Recombination/Generation(RG) method:</div><div><br></div><div>The non-equilibrium Green function (NEGF) method is capable of nanodevice performance predictions including coherent and incoherent effects. To treat incoherent scattering, carrier generation and recombination is computationally very expensive. In this work, the numerically efficient Büttiker-probe model is expanded to cover recombination and generation effects in addition to various incoherent scattering processes. The capability of the new method to predict nanodevices is exemplified with quantum well III-N light-emitting diodes and photo-detector. Comparison is made with the state of art drift-diffusion method. Agreements are found to justify the method and disagreements are identified attributing to quantum effects. </div><div><br></div><div>The two menthod are individually developed and utilized together to study BP/MoS2 interface. In this vertical 2D device, anti-ambipolar(AAP) IV curve has been identified experimentally with different explanation in the current literature. An atomistic simulation is performed with basis generated from density functional theory. Recombination process is included and is able to explain the experiment findings and to provide insights into 2D interface devices.</div><div><br></div><div> </div>

<p dir="ltr">Photovoltaics are leading devices in green energy production. Understanding the fundamental physics behind energy transport in candidate materials for future photovoltaic and optoelectronic devices is necessary to both realize material limitations and improve efficiency. Excitons, which are bound electron-hole pairs, are central to determining how energy propagates throughout semiconductors. Exciton transport is greatly influenced by material dimensionality. In highly ordered quantum dot (QD) systems, electronic coupling between individual QDs can lead to coherent exciton transport, whereas in two-dimensional heterostructures, excitons can form at the interface of a heterojunction, creating charge-transfer excitons.</p><p dir="ltr">This dissertation is dedicated to summarizing the studies of exciton transport and behavior in two systems: perovskite QD superlattices and transition metal dichalcogenide (TMDC)/polyacene heterostructures. Chapter 1 provides readers with details on these materials in addition to information on the fundamental concepts (i.e., excitons, phonons, energy transfer) needed to best appreciate further chapters. Chapter 2 summarizes the spectroscopic techniques (photoluminescence and transient absorption spectroscopy and microscopy) used to examine exciton behavior. Next, the effects of disorder and dephasing pathways on the ability of perovskite QDs to coherently couple is investigated through the lens of superradiance in Chapter 3. After this, the temperature-dependent exciton transport within perovskite QD superlattices is imaged with high spatial and temporal resolutions in Chapter 4. The experimental transport data on these superlattices provides evidence for environment-assisted quantum transport, which, until this study, had yet to be realized in solid-state systems. In Chapter 5, attention is switched to verifying the existence and deepening the understanding of the behavior of several spatially separated interlayer excitons in a tungsten disulfide/tetracene heterostructure. Finally, Chapter 6 summarizes the preliminary results obtained through transient absorption spectroscopy on other TMDC/polyacene heterostructures where separation of the triplet pair state is attempted. </p><p dir="ltr">It is this author’s hope that this dissertation will not only summarize their graduate work but will also serve as inspiration for others to continue learning and contribute to the advancement of the energy research field.</p>

Various nanostructured materials display unique and interesting optical properties. Specific nanoscale objects discussed in an experimental perspective in this dissertation include optical metamaterials, surface plasmon sensors, and two-dimensional materials. These nanoscale objects were fabricated, investigated optically, and their applications are assessed. First, one-dimensional magnetic gratings were studied, followed by their two-dimensional analog, the so-called "fishnet." Both were fabricated, characterized, and their properties, such as waveguiding modes, are examined. Interestingly, these devices can exhibit optical magnetism and even negative refraction; however, their general characterization at oblique incidence is challenging due to diffraction. Here, a new method of optical characterization of metamaterials which takes into account diffraction is presented. Next, surface plasmon resonance (SPR) was experimentally used in two schemes, for the first time, to determine the transition layer characteristics between a metal and dielectric. The physics of interfaces, namely the singularity of electric permittivity and how it can be electrically shifted, becomes clearer owing to the extreme sensitivity of SPR detection mechanisms. Finally, ultra-thin two-dimensional semiconducting materials had their radiative lifetime analyzed. Their lifetimes are tuned both by number of atomic layers and applied voltage biasing across the surface, and the changes in lifetime are suspected to be due to quenching or enhancement of non-radiative process rates.

No description available.