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Abstract: The thermochromic properties of vanadium dioxide (VO2) offer great advantages for energy-saving smart windows, memory devices, and transistors. However, the crystallization of solution-based thin films at temperatures lower than 400°C remains a challenge. Photonic annealing has recently been exploited to crystallize metal oxides, with minimal thermal damage to the substrate and reduced manufacturing time. Here, VO2 thin films, obtained via a green sol-gel process, were crystallized by pulsed excimer laser annealing. The influence of increasing laser fluence and pulse number on the film properties was systematically studied through optical, structural, morphological, and chemical characterizations. From temperature profile simulations, the temperature rise was confirmed to be confined within the film during the laser pulses, with negligible substrate heating. Threshold laser parameters to induce VO2 crystallization without surface melting were found. With respect to furnace annealing, both the crystallization temperature and the annealing time were substantially reduced, with VO2 crystallization being achieved within only 60 s of laser exposure. The laser processing was performed at room temperature in air, without the need of a controlled atmosphere. The thermochromic properties of the lasered thin films were comparable with the reference furnace-treated samples.

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Abstract: The discovery of ferroelectricity in CMOS-compatible oxides, such as doped hafnium oxide, has opened new possibilities for electronics by reviving the use of ferroelectric implementations on modern technology platforms. This thesis presents the ground-up integration of ferroelectric HfO2 on a thermally sensitive III-V nanowire platform leading to the successful implementation of ferroelectric transistors (FeFETs), tunnel junctions (FTJs), and varactors for mm-wave applications. As ferroelectric HfO2 on III-V semiconductors is a nascent technology, a special emphasis is put on the fundamental integration issues and the various engineering challenges facing the technology. The fabrication of metal-oxide-semiconductor (MOS) capacitors is treated as well as the measurement methods developed to investigate the interfacial quality to the narrow bandgap III-V materials using both electrical and operando synchrotron light source techniques. After optimizing both the films and the top electrode, the gate stack is integrated onto vertical InAs nanowires on Si in order to successfully implement FeFETs. Their performance and reliability can be explained from the deeper physical understanding obtained from the capacitor structures. By introducing an InAs/(In)GaAsSb/GaSb heterostructure in the nanowire, a ferroelectric tunnel field effect transistor (ferro-TFET) is fabricated. Based on the ultra-short effective channel created by the band-to-band tunneling process, the localized potential variations induced by single ultra-scaled ferroelectric domains and individual defects are sensed and investigated. By intentionally introducing a gate-source overlap in the ferro-TFET, a non-volatile reconfigurable single-transistor solution for modulating an input signal with diverse modes including signal transmission, phase shift, frequency doubling, and mixing is implemented. Finally, by fabricating scaled ferroelectric MOS capacitors in the front-end with a dedicated and adopted RF and mm-wave backend-of-line (BEOL) implementation, the ferroelectric behavior is captured at RF and mm-wave frequencies.

Open Access

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Abstract: The desire to increase the energy density of stoichiometric layered Li TM O 2 (TM = 3d transition metal) cathode materials has promoted investigation into their properties at high states of charge. Although there is increasing evidence for pronounced oxygen participation in the charge compensation mechanism, questions remain whether this is true O -redox, as observed in Li -excess cathodes. Through a high-resolution O K-edge resonant inelastic x-ray spectroscopy (RIXS) study of the Mn -free Ni -rich layered oxide Li Ni 0.98 W 0.02 O 2 , we demonstrate that the same oxidized oxygen environment exists in both Li -excess and non- Li -excess systems. The observation of identical RIXS loss features in both classes of compounds is remarkable given the differences in their crystallographic structure and delithiation pathways. This lack of a specific structural motif reveals the importance of electron correlation in the charge compensation mechanism for these systems and indicates how a better description of charge compensation in layered oxides is required to understand anionic redox for energy storage.

Open Access

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Abstract: A comprehensive study of bulk molybdenum dichalcogenides is presented with the use of soft and hard X-ray photoelectron (SXPS and HAXPES) spectroscopy combined with hybrid density functional theory (DFT). The main core levels of MoS2, MoSe2, and MoTe2 are explored. Laboratory-based X-ray photoelectron spectroscopy (XPS) is used to determine the ionization potential (IP) values of the MoX2 series as 5.86, 5.40, and 5.00 eV for MoSe2, MoSe2, and MoTe2, respectively, enabling the band alignment of the series to be established. Finally, the valence band measurements are compared with the calculated density of states which shows the role of p-d hybridization in these materials. Down the group, an increase in the p-d hybridization from the sulfide to the telluride is observed, explained by the configuration energy of the chalcogen p orbitals becoming closer to that of the valence Mo 4d orbitals. This pushes the valence band maximum closer to the vacuum level, explaining the decreasing IP down the series. High-resolution SXPS and HAXPES core-level spectra address the shortcomings of the XPS analysis in the literature. Furthermore, the experimentally determined band alignment can be used to inform future device work.

Open Access

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Abstract: Understanding a material’s electronic structure is crucial to the development of many functional devices from semiconductors to solar cells and Li-ion batteries. A material’s properties, including electronic structure, are dependent on the arrangement of its atoms. However, structure determination (the process of uncovering the atomic arrangement), is impeded, both experimentally and computationally, by disorder. The lack of a verifiable atomic model presents a huge challenge when designing functional amorphous materials. Such materials may be characterised through their local atomic environments using, for example, solid-state NMR and XAS. By using these two spectroscopy methods to inform the sampling of configurations from ab initio molecular dynamics we devise and validate an amorphous model, choosing amorphous alumina to illustrate the approach due to its wide range of technological uses. Our model predicts two distinct geometric environments of AlO5 coordination polyhedra and determines the origin of the pre-edge features in the Al K-edge XAS. From our model we construct an average electronic density of states for amorphous alumina, and identify localized states at the conduction band minimum (CBM). We show that the presence of a pre-edge peak in the XAS is a result of transitions from the Al 1s to Al 3s states at the CBM. Deconvoluting this XAS by coordination geometry reveals contributions from both AlO4 and AlO5 geometries at the CBM give rise to the pre-edge, which provides insight into the role of AlO5 in the electronic structure of alumina. This work represents an important advance within the field of solid-state amorphous modelling, providing a method for developing amorphous models through the comparison of experimental and computationally derived spectra, which may then be used to determine the electronic structure of amorphous materials.