Supported catalytic nanoparticles undergo rapid structural transformations faster than many transmission electron microscopes (TEMs) can track. This is the case with platinum nanoparticles supported on cerium oxide (Pt/CeO2) in a CO and O2 gaseous environment. By furthering our understanding of the structural dynamics of the Pt/CeO2 system, improved catalyst design principles may be derived to enhance the efficiency of this catalyst. Developing static models of a 2 nm Pt nanoparticle supported on CeO2 and simulating TEM images of the models was found to create similar images to those seen in experimental TEM time-resolved series of the system. Rotations of static models on a ceria support provides a way to understand the experimental samples in three dimensions, which is difficult in two dimensional TEM images. This project expands the possibilities of interpreting TEM images of catalytic systems.
Anatase exists often in its reduced form (TiO2-x), enabling it to perform redox reactions through the absorption and release of oxygen into/from the crystal lattice. These processes result in structural changes, induced by defects in the material, which can theoretically be observed using advanced characterization methods. In situ electron microscopy is one of such methods, and can provide a window into these structural changes. However, in order to interpret the structural evolution caused by defects in materials, it is often necessary and pertinent to use atomistic simulations to compare the experimental images with models.
In this thesis project, we modeled the defect structures in anatase, around oxygen vacancies and at surfaces, using molecular dynamics, benchmarked with density functional theory. Using a “reactive” forcefield designed for the simulation of interactions between anatase and water that can model and treat bonding through the use of bond orders, different vacancy structures were analyzed and simulated. To compare these theoretical, generated models with experimental data, the “multislice approach” to TEM image simulation was used. We investigated a series of different vacancy configurations and surfaces and generated fingerprints for comparison with TEM experiments. This comparison demonstrated a proof of concept for a technique suggesting the possibility for the identification of oxygen vacancy structures directly from TEM images. This research aims to improve our atomic-level understanding of oxide materials, by providing a methodology for the analysis of vacancy formation from very subtle phenomena in TEM images.
A model Ni/CeO2 catalyst was used to probe the role of a ceria support during hydrocarbon reforming reactions, and it was revealed that carbon formation was inhibited on Ni metal nanoparticles due to the removal of lattice oxygen from the ceria support and subsequent oxidation of adsorbed decomposed hydrocarbon products. Atomic resolution observations of surface oxygen vacancy creation and annihilation were performed on CeO2 nanoparticle surfaces using a novel time-resolved in situ AC-TEM approach. Cation displacements were found to be related to oxygen vacancy creation and annihilation, and the most reactive surface oxygen sites were identified by monitoring the frequency of cation displacements. In addition, the dynamic evolution of CeO2 surface structures was characterized with high temporal resolution AC-TEM imaging, which resulted in atomic column positions and occupancies to be determined with a combination of spatial precision and temporal resolution that had not previously been achieved. As a result, local lattice expansions and contractions were observed on ceria surfaces, which were likely related to cyclic oxygen vacancy activity. Finally, local strain fields on CeO2 surfaces were quantified, and it was determined that local strain enhanced the ability of a surface site to create oxygen vacancies. Through the characterization of dynamic surface structures with advanced AC-TEM techniques, an improvement in the fundamental understanding of how ceria surfaces influence and control oxygen exchange reactions was obtained.
210 nm thick InAsSbBi layers grown at temperatures from 280 °C to 430 °C on (100) on-axis, (100) offcut 1° to (011), and (100) offcut 4° to (111)A GaSb substrates are investigated using Rutherford back scattering, X-ray diffraction, transmission electron microscopy, Nomarski optical microscopy, atomic force microscopy, and photoluminescence spectroscopy. The results indicate that the layers are coherently strained and contain dilute Bi mole fractions.
Large surface droplets with diameters and densities on the order of 3 µm and 106 cm-2 are observed when the growth is performed with As overpressures around 1%. Preferential orientation of the droplets occurs along the [011 ̅] step edges offcut (100) 1° to (011) substrate. The surface droplets are not observed when the As overpressure is increased to 4%. Small crystalline droplets with diameters and densities on the order of 70 nm and 1010 cm-2 are observed between the large droplets for the growth at 430°C. Analysis of one of the small droplets indicates a misoriented zinc blende structure composed of In, Sb, and Bi, with a 6.543 ± 0.038 Å lattice constant.
Lateral variation in the Bi mole fraction is observed in InAsSbBi grown at high temperature (400 °C, 420 °C) on (100) on-axis and (100) offcut 4° to (111)A substrates, but is not observed for growth at 280 °C or on (100) substrates that are offcut 1° to (011). Improved crystal and optical quality is observed in the high temperature grown InAsSbBi and CuPtB type atomic ordering on the {111}B planes is observed in the low temperature grown InAsSbBi. Strain induced tilt is observed in coherently strained InAsSbBi grown on offcut substrates.
An extensive effort was made to identify specific locations of crystal defects in epitaxial CdTe that might contribute to degraded light-conversion efficiency. Electroluminescence (EL) mapping and the creation of surface etch pits through chemical treatment were combined in attempts to identify specific structural defects for subsequent TEM examination. Observations of these specimens revealed only surface etch pits, without any visible indication of extended defects near their base. While chemical etch pits could be helpful for precisely locating extended defects that intersect with the treated surface, this study concluded that surface roughness surrounding etch pits would likely mitigate against their usefulness.
Defect locations in GaAs solar-cell devices were identified using combinations of EL, photoluminescence, and Raman scattering, and then studied more closely using TEM. Observations showed that device degradation was invariably associated with a cluster of extended defects, rather than a single defect, as previously assumed. AC-STEM observations revealed that individual defects within each cluster consisted primarily of intrinsic stacking faults terminated by 30° and 90° partial dislocations, although other defect structures were also identified. Lomer dislocations were identified near locations where two lines of strain contrast intersected in a large cluster, and a comparatively shallow cluster, largely constrained to the GaAs emitter layer, contained 60° perfect dislocations associated with localized strain contrast.
In another study, misfit dislocations at II-VI/III-V heterovalent interfaces were investigated and characterized using AC-STEM. Misfit strain at ZnTe/GaAs interfaces, which have relatively high lattice mismatch (7.38%), was relieved primarily through Lomer dislocations, while ZnTe/InP interfaces, with only 3.85% lattice mismatch, were relaxed by a mixture of 60° perfect dislocations, 30° partial dislocations, and Lomer dislocations. These results were consistent with the previous findings that misfit strain was relaxed primarily through 60° perfect dislocations that had either dissociated into partial dislocations or interacted to form Lomer dislocations as the amount of misfit strain increased.
Electron energy-loss spectroscopy (EELS) is used to sense variations in the local concentration of amine moieties (defects believed to facilitate interfacial charge transfer) at the surface of a g-CNxHy flake. Using an aloof-beam configuration, spatial resolution is maximized while minimizing damage thus providing nanoscale vibrational fingerprints similar to infrared absorption spectra. Structural disorder in g-CNxHys is further studied using transmission electron microscopy at low electron fluence rates. In-plane structural fluctuations revealed variations in the local azimuthal orientation of the heptazine building blocks, allowing planar domain sizes to be related to the average polymer chain length. Furthermore, competing factors regulating photocatalytic performance in a series of Pt/g-CNxHys is elucidated. Increased polymer condensation in the g-CNxHy support enhances the rate of charge transfer to reactants owing to higher electronic mobility. However, active site densities are over 3x lower on the most condensed g-CNxHy which ultimately limits its H2 evolution rate (HER). Based on these findings, strategies to improve the cocatalyst configuration on intrinsically active supports are given.
In TiO2/CeO2-x photocatalysts, the effect of the support particle size on the bulk
anoscale properties and photocatalytic performance is investigated. Small anatase supports facilitate highly dispersed CeO2-x species, leading to increased visible light absorption and HERs resulting from a higher density of mixed metal oxide (MMO) interfaces with Ce3+ species. Using monochromated EELS, bandgap states associated with MMO interfaces are detected, revealing electronic transitions from 0.5 eV up to the bulk bandgap onset of anatase. Overall, the electron microscopy/spectroscopy techniques developed and applied herein sheds light onto the relevant defects and limiting processes operating within these photocatalyst systems thus suggesting rational design strategies.