The effect of temperature on bubble lattice formation in copper under in situ He ion irradiation

In situ ion irradiation in a transmission electron microscope was used to investigate the effects of temperature on radiation-induced bubble lattice formation in Cu by low energy (12 keV) helium ions. Bubble lattices were observed to form between − 100 and 100 °C, but at 200 °C lattice formation was impeded by continued growth and agglomeration of bubbles. Both nucleation of bubbles, and to a lesser extent bubble lattice formation, are observed at lower fluences as temperature increases, which we suggest is due to increased point defect mobility. Previous work on point defect concentrations in irradiated copper is considered when interpreting these results

Removal and Reoccurrence of LLZTO Surface Contaminants under Glovebox Conditions

The reactivity of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) solid electrolytes to form lithio-phobic species such as Li2CO3 on their surface when exposed to trace amounts of H2O and CO2 limits the progress of LLZTO-based solid-state batteries. Various treatments, such as annealing LLZTO within a glovebox or acid etching, aim at removing the surface contaminants, but a comprehensive understanding of the evolving LLZTO surface chemistry during and after these treatments is lacking. Here, glovebox-like H2O and CO2 conditions were recreated in a near ambient pressure X-ray photoelectron spectroscopy chamber to analyze the LLZTO surface under realistic conditions. We find that annealing LLZTO at 600 °C in this atmosphere effectively removes the surface contaminants, but a significant level of contamination reappears upon cooling down. In contrast, HCl(aq) acid etching demonstrates superior Li2CO3 removal and stable surface chemistry post treatment. To avoid air exposure during the acid treatment, an anhydrous HCl solution in diethyl ether was used directly within the glovebox. This novel acid etching strategy delivers the lowest lithium/LLZTO interfacial resistance and the highest critical current density

Initiation of dendritic failure of LLZTO via sub-surface lithium deposition

The occurrence of lithium deposition in occluded spaces within ceramic electrolytes due to electronic leakage currents can jeopardise the commercialization of power-dense solid-state batteries. Here, we utilize plasma-FIB serial sectioning to visualize the surface and sub-surface of a garnet solid electrolyte (LLZTO) after lithium plating. We study the morphology of surface spallation cracks, which represent the initial stage of dendrite formation. Employing a LiMg anode, we track the magnesium diffusion around these surface cracks with EDS. The absence of magnesium in early-stage cracks suggests they form due to the pressure build-up from the deposition of pure lithium in occluded pores near the electrolyte surface. These spallation cracks act as current focusing and stress concentration hot spots. Electron beam induced current imaging demonstrates that short-circuiting lithium dendrites grow from the spallations during plating. Thus, the sub-surface deposition of lithium is a possible explanation for the initiation of lithium dendrites in LLZTO

Revealing the role of fluoride‐rich battery electrode interphases by operando transmission electron microscopy

The solid electrolyte interphase (SEI), a complex layer that forms over the surface of electrodes exposed to battery electrolyte, has a central influence on the structural evolution of the electrode during battery operation. For lithium metallic anodes, tailoring this SEI is regarded as one of the most effective avenues for ensuring consistent cycling behavior, and thus practical efficiencies. While fluoride-rich interphases in particular seem beneficial, how they alter the structural dynamics of lithium plating and stripping to promote efficiency remains only partly understood. Here, operando liquid-cell transmission electron microscopy is used to investigate the nanoscale structural evolution of lithium electrodeposition and dissolution at the electrode surface across fluoride-poor and fluoride-rich interphases. The in situ imaging of lithium cycling reveals that a fluoride-rich SEI yields a denser Li structure that is particularly amenable to uniform stripping, thus suppressing lithium detachment and isolation. By combination with quantitative composition analysis via mass spectrometry, it is identified that the fluoride-rich SEI suppresses overall lithium loss through drastically reducing the quantity of dead Li formation and preventing electrolyte decomposition. These findings highlight the importance of appropriately tailoring the SEI for facilitating consistent and uniform lithium dissolution, and its potent role in governing the plated lithium's structure

Time-of-flight secondary ion mass spectrometry - fundamental issues for quantitative measurements and multivariate data analysis

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a powerful technique for the analysis of organic surfaces and interfaces for many innovative technologies. However, despite recent developments, there are still many issues and challenges hindering the robust, validated use of ToF-SIMS for quantitative measurement. These include: the lack of metrology and fundamental understanding for the use of novel cluster primary ion beams such as C60n+ and Ar2000+; the need for validated and robust measurement protocols for difficult samples, such as those with significant micron scale surface topography; the lack of guidance on novel data analysis methods including multivariate analysis which have the potential to simplify many time-consuming and intensive analyses in industry; and the need to establish best practice to improve the accuracy of measurements. This thesis describes research undertaken to address the above challenges. Sample topography and field effects were evaluated experimentally using model conducting and insulating fibres and compared with computer simulations to provide recommendation to diagnose and reduce the effects. Two popular multivariate methods, principal component analysis (PCA) and multivariate curve resolution (MCR), were explored using mixed organic systems consisting of a simple polymer blend and complex hair fibres treated with a multi-component formulation to evaluate different multivariate and data preprocessing methods for the optimal identification, localisation and quantification of the chemical components. Finally, cluster ion beams C60n+ and Ar500-2500+ were evaluated on an inorganic surface and an organic delta layer reference material respectively to elucidate the fundamental metrology of cluster ion sputtering and pave the way for their use in organic depth profiling. These studies provide the essential metrological foundation to address frontier issues in surface and nanoanalysis and extend the measurement capabilities of ToF-SIMS.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Preparation, microstructure and microwave dielectric properties of sprayed PFA/barium titanate composite films

Frequency dependence of the dielectric properties of polymer-ferroelectric composites at different bands of microwave frequencies was investigated in this work. Perfluoroalkoxy (PFA)/barium titanate (BaTiO3) nanocomposite films were prepared by spray deposition. The spraying process was scaled up to fabricate large area (max. 160 mm × 160 mm) uniform composite sheets out of which a controlled bonding process was introduced to form composite blocks. The microstructure of the composite films was examined by SEM with a microtome sample preparation method to evaluate the effectiveness of the spraying process at producing uniform particle distributions. The dielectric properties of the composite films with various BaTiO3 loadings were characterised by an Impedance Analyzer at frequencies between 10 Hz and 1 MHz and Vector Network Analyzer at 12–18 GHz respectively. The Lichtenecker mixing rule was incorporated to fit the measured dielectric constant data, which gives estimates of dielectric constant of the BaTiO3 nanometer sized particles to be 895 and 571 at 10 kHz and 15 GHz respectively. In comparison, the composite effective dielectric constant was approximately reduced by 25% at 10 kHz than that at 15 GHz

Electrical, photoelectrical and morphological properties of ZnO nanofiber networks grown on SiO2 and on Si nanowires

ZnO nanofibre networks (NFNs) were grown by vapour transport method on Si-based substrates. One type of substrate was SiO2 thermally grown on Si and another consisted of a Si wafer onto which Si nanowires (NWs) had been grown having Au nanoparticles catalysts. The ZnO-NFN morphology was observed by scanning electron microscopy on samples grown at 600 °C and 720 °C substrate temperature, while an focused ion beam was used to study the ZnO NFN/Si NWs/Si and ZnO NFN/SiO2 interfaces. Photoluminescence, electrical conductance and photoconductance of ZnO-NFN was studied for the sample grown on SiO2. The photoluminescence spectra show strong peaks due to exciton recombination and lattice defects. The ZnO-NFN presents quasi-persistent photoconductivity effects and ohmic I-V characteristics which become nonlinear and hysteretic as the applied voltage is increased. The electrical conductance as a function of temperature can be described by a modified three dimensional variable hopping model with nanometer-ranged typical hopping distances

In-situ TEM study of irradiation-induced damage mechanisms in monoclinic-ZrO2

We have investigated the microstructural and crystallographic evolution of nanocrystalline zirconia under heavy ion irradiation using in-situ transmission electron microscopy (TEM) and have studied the atomic configurations of defect clusters using aberration-corrected scanning transmission electron microscopy (STEM). Under heavy ion irradiation the monoclinic-ZrO2 is observed to transform into cubic phase, stabilised by the strain induced by irradiation-induced defect clusters. We suggest that the monoclinic-to-cubic transformation is martensitic in nature with an orientation relationship identified to be (100)m∥(100)c and [001]m∥[001]c. By increasing the damage dose, both the formation of voids and irradiation-induced grain growth were observed. A model for the formation of voids is proposed, taking defect interactions into consideration. The study has also demonstrated that high resolution orientation mapping by transmission Kikuchi diffraction (TKD) combined with in-situ irradiation in a TEM is a powerful method to probe the mechanisms controlling irradiation-induced processes, including grain boundary migration, phase transformations and texture evolution