Sodium-ion batteries (SIBs) are considered as a promising alternative to lithium-ion batteries (LIBs) for large-scale renewable energy storage units due to the abundance of sodium resource and its low cost. However, the development of anode materials for SIBs to date has been mainly limited to some traditional anodes for LIBs, such as carbonaceous materials. SnSe2 is a member of two dimensional layered transition metal dichalcogenide (TMD) family, which has been predicted to have high theoretical capacity as anode material for sodium ion batteries (756 mAh g-1), thanks to its layered crystal structure. Yet, there have been no studies on using SnSe2 as Na ion battery anode. In this thesis, we developed a simple synthesis method to prepare pure SnSe2 nanosheets, employing N2 saturated NaHSe solution as a new selenium source. The SnSe2 2D sheets achieve theoretical capacity during the first cycle, and a stable and reversible specific capacity of 515 mAh g-1 at 0.1 A g-1 after 100 cycles, with excellent rate performance. Among all of the reported transition metal selenides, our SnSe2 sample has the highest reversible capacity and the best rate performances. A combination of ex-situ high resolution transmission electron microscopy (HRTEM) and X-ray diffraction was used to study the mechanism of sodiation and desodiation process in this SnSe2, and to understand the reason for the excellent results that we have obtained. The analysis indicate that a combination of conversion and alloying reactions take place with SnSe2 anodes during battery operation, which helps to explain the high capacity of SnSe2 anodes for SIBs compared to other binary selenides. Density functional theory was used to elucidate the volume changes taking place in this important 2D material.

In this thesis, the growth of 2D materials, in particular graphene and FeO2 on crystalline supports, is studied by a multitude of surface-sensitive techniques. The mechanisms of graphene growth in ultra-high vacuum and high Ar pressure are explored, and a simple device for the manufacturing of high-quality, monocrystalline graphene on SiC is described. The electronic and chemical properties of B and N dopants on graphene are characterized by means of STM/AFM with CO-functionalized tips and supported by DFT calculations. The chemical interaction of a probe molecule (FePc) with doped graphene is also investigated. The long-standing controversy of the so-called "biphase" reconstruction of α - Fe2O3(0001) is resolved by the discovery of a complete FeO2 overlayer in this phase. The structure of this overlayer is investigated by means of STM, LEEM and DFT calculations. A thorough description of the routes to obtain single phases over the whole surface of α - Fe2O3(0001) is provided.

No description available.

Investigates the mechanical and electronic properties of two-dimensional nanomaterials under strain, addressing gaps in the existing literature. The primary challenge with these materials is the inconsistent application of high strain rates and the absence of experimental data at low temperatures. To overcome these challenges, we develop Microelectromechanical Systems (MEMS)-based devices for characterizing 2D nanomaterials and semiconductor materials at low temperatures. Four MEMS-based devices are developed to facilitate this characterization. The first device is a unique MEMS testing platform with on-chip actuation, sensing, and feedback control systems, capable of applying controlled displacements to nanoscale specimens while minimizing temperature fluctuations. To achieve this, MEMS thermal actuators with an axial stiffness of 40253.6 N/m are used. Capacitive sensors and V-beam amplification mechanisms are designed for precise measurement. The second device, the cascaded MEMS device, employs horizontal and vertical V-shaped structures to measure stress-strain curves of 2D nanomaterials at low temperatures. The third device is a customized MEMS electrostatic actuator for bending tests on silicon material under low-temperature conditions. Finally, two MEMS rotational structures, including a novel C-shaped structure, are developed to amplify movement. The MEMS devices are fabricated using bulk micromachining and deep reactive-ion etching (DRIE) with silicon-on-insulator (SOI) wafers, incorporating underpass technology for electrical isolation within the MEMS-based testing platforms. To optimize DRIE etching parameters for creating underpass islands in SOI MEMS, a study was conducted considering a total of nine wafers, divided into two batches for fabrication process, and examining their behavior concerning the etching process. The devices are optically characterized at room temperature and tested in a vacuum environment and at low temperatures using scanning tunneling microscope (STM) tool.

No description available.

In the present thesis, research work to tackle challenges such as large-scale integration, selectivity and low efficiency around different types of nanocarbon based sensors is performed. The findings of these studies are given in the form of peer-reviewed publications and conclusions with future recommendations proposed as a summary. The work focuses on three key sensors types, gas sensors, biosensors and photodetectors. The first key aspect is dielectrophoretic (DEP) deposition of nitrogen doped single-walled carbon nanotubes (N-SWCNTs) and it is used as a route to large-scale assembly of increased reactivity, and thus selectivity, gas sensors. Furthermore, suspended SWCNTs and few layer graphene (FLG) devices are fabricated through a novel process which results in increased surface area transducers and low resistance SWCNTs based devices. Moreover, biosensors face similar challenges to gas sensors with the addition that their selectivity needs to be engineered through the formation of a biomimetic interface due to the nature of the analytes they are destined to investigate. Non-covalent functionalization of graphene using self-assembled phospholipid membranes delivered in a controlled and precise manner by dip-pen nanolithography (DPN) was demonstrated together with a high-speed fabrication process of bioassays onto patterned CVD graphene using a parallel tips system. Lastly, for the case of photodetectors, a SWCNT – nanoplasmonic system is proposed as a solution to the major issue of low quantum efficiency in low dimensionality materials. First, the performance of various geometries and arrangements of Au nanoparticles is explored by transferring a micromechanically exfoliated graphene flake onto them and studying the Raman enhancement that arises due to uncoupled and coupled near-fields. An increase of graphene Raman signal of 103 was observed for the areas suspended between two closely spaced dimers as a result of strong near field coupling when the polarisation of the incident light is parallel to the nanostructures axis. A large-scale integration of SWCNTs positioned in between the dimers using DEP is performed as a demonstration of the scalability of the system.

Monolayers and heterostructures of two-dimensional (2D) electronic materials with spin-orbit interactions offer the promise of observing many novel physical effects. While theoretical predictions of 2D layered materials based on density functional theory (DFT) are many, the DFT approach is limited to small simulation sizes (several nanometers), and thus inhomogeneous strain and boundary effects that are often observed experimentally cannot be simulated within a reasonable time. The aim of this thesis is (i) to study effects of strain on 2D materials beyond graphene using first-principles and tight-binding methods and (ii) to investigate the effects of cuts--"kirigami"-- on 2D materials using molecular dynamics and machine learning approach. The first half of this thesis focuses on the effects of strain on manipulating spin and valley degrees of freedom for two classes of 2D materials--monochalcogenide and lead chalcogenide monolayers--using DFT. A tight-binding (TB) approach is developed to describe the electronic changes in lead chalcogenide monolayers due to strains that often persist in real devices. The strain-dependent TB model allows one to establish a relationship between the Rashba field and the out-of-plane strain or electric polarization from a microscopic view, a connection that is not well understood in the ferroelectric Rashba materials. This framework connecting strain fields and electronic changes is important to overcome the size and computational limitations associated with DFT. The second part of the thesis focuses on defect engineering and design of 2D materials via the "kirigami" technique of introducing different patterns of cuts. A machine learning (ML) approach is presented to provide physical insights and an effective model to describe the physical system. We demonstrate that a machine learning model based on a convolutional neural network is able to find the optimal design from a training data set that is much smaller than the design space.

This thesis describes a detailed study of advanced fibre optic sensors and their applications for label-free biochemical detection. The major contributions presented in this thesis are summarised below. A self-assembly based in-situ layer-by-layer (i-LbL) or multilayer deposition technique has been developed to deposit the 2D material nanosheets on cylindrical fibre devices. This deposition technique is based on the chemical bonding associated with the physical adsorption, securing high-quality 2D materials coating on specific fibre cylindrical surface with strong adhesion as well as a prospective thickness control. Then a " Photonic-nano-bio configuration", which is bioprobes immobilised 2D-(nano)material deposited fibre grating, was built. 2D material overlay provides a remarkable analytical platform for bio-affinity binding interface due to its exceptional optical and biochemical properties. EDC (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide) and NHS (NHydroxysuccinimide) were used to immobilise bioprobes. This kind of configuration is considered to have many advantages such as: enhanced RI sensitivity, enrich immobilisation sites, improved binding efficiency, selective detection. Followed by this configuration, several label-free biosensors were developed. For example, graphene oxide coated dual-peak long period grating (GO-dLPG) based immunosensor has been implemented for ultrasensitive detection of antibody/antigen interaction. The GO-LPG based biosensor has been developed for label-free haemoglobin detection. Apart from biosensors, the black phosphorus (BP) integrated tilted fibre grating (TFG) has been proposed, for the first time, as BP-fibre optic chemical sensor for heavy metal (Pb2+ ions) detection, demonstrating ultrahigh sensitivity, lower limit of detection and wider concentration range. Ultrafast laser micromachining technology has been employed to fabricate long period grating (LPG) and microstructures on optical fibre. The ultrafast laser micromachined polymer optical fibre Bragg grating (POFBG) has been developed for humidity sensing, showing the significant improvement with the reduced response time.

Graphene and other two-dimensional materials can be stacked together to form vander Waals heterostructures: synthetic crystals composed of different atomically thin layers with a bespoke electronic band structure. Structural characterisation of vander Waals heterostructures is difficult using conventional methods as the properties are almost entirely defined by the nature of the buried interfaces between dissimilar crystals. These methods also fall short of resolving the atomic structure of buried defects in van der Waals materials such as graphite. This work demonstrates the refinement and successful application of ion beam specimen preparation to produce cross sectional slices through these unique crystals so that they can be characterised by high resolution scanning transmission electron microscopy (STEM). Cross sectional specimen were prepared using in situ lift-out in a focused ion beam (FIB) dual-beam instrument. The fine polishing steps were optimised to prevent damage to the core of the specimen. High resolution STEM imaging of twin defects in graphene, hexagonal boron ni-tride and MoSe2 revealed that the boundaries are not atomically sharp but extended across many atoms. Advanced processing and analysis of these images uncovered fundamental mechanics which govern their geometry. This technique was further applied to complex transition metal dichalcogenide heterostructures to quantitatively determine the properties of buried interfaces between atomically thin crystals.

This thesis explores the use of 2D materials (graphene and hBN) for spintronics. Interest on these materials in spintronics arose from theoretical predictions of high spin filtering in out-of-plane transport through graphene and hBN sandwiched by ferromagnets. Similarly, 5-layer graphene was forecast to be a perfect spin filter. In the case of in-plane spin transport, graphene was expected to be an excellent material due to its low spin-orbit coupling and low number of defects. Although there already exist experimental works that attempted to explore the aforementioned predictions, they have failed so far to comply with the expected results. Earlier experimental works in graphene and hBN out-of-plane spin transport achieved low spin filtering on the order of a few percent; while spin relaxation parameters in graphene for in-plane spin transport remained one or two orders of magnitude below the predicted values. In the case of vertical devices, the failure to meet the theoretical expectations was attributed to the oxidation of the ferromagnets and the lack of an epitaxial interface between the later and the graphene or hBN. Similarly, the exact mechanisms that lead to high spin relaxation for in-plane spin transport in graphene are not completely understood, in part due to the low-quality of the explored devices. In this thesis we analyze new architectures and procedures that allowed us to fabricate ultraclean and oxidation-free interfaces between ferromagnets and graphene or hBN. In these devices we encountered negative and reversible magnetoresistance, that could not be explained with the previous theoretical models. We propose a new model based on a thorough characterization of the devices and well-known properties of graphene that were not taken into account in the previous model. We also employed a novel type of contact to graphene (1D-contacts) and applied it for the first time to achieve spin-injection in graphene. The main advantage of this type of contact is the full encapsulation of graphene with hBN, which leads to high quality graphene spintronic devices.