Matching Items (21)

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TEM Image Simulations of Structural Dynamics on CeO2-supported Pt Catalysts

Description

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

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.

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  • 2021-05

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Structural and optical properties of II-VI and III-V compound semiconductors

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This dissertation is on the study of structural and optical properties of some III-V and II-VI compound semiconductors. The first part of this dissertation is a study of the deformation

This dissertation is on the study of structural and optical properties of some III-V and II-VI compound semiconductors. The first part of this dissertation is a study of the deformation mechanisms associated with nanoindentation and nanoscratching of InP, GaN, and ZnO crystals. The second part is an investigation of some fundamental issues regarding compositional fluctuations and microstructure in GaInNAs and InAlN alloys. In the first part, the microstructure of (001) InP scratched in an atomic force microscope with a small diamond tip has been studied as a function of applied normal force and crystalline direction in order to understand at the nanometer scale the deformation mechanisms in the zinc-blende structure. TEM images show deeper dislocation propagation for scratches along <110> compared to <100>. High strain fields were observed in <100> scratches, indicating hardening due to locking of dislocations gliding on different slip planes. Reverse plastic flow have been observed in <110> scratches in the form of pop-up events that result from recovery of stored elastic strain. In a separate study, nanoindentation-induced plastic deformation has been studied in c-, a-, and m-plane ZnO single crystals and c-plane GaN respectively, to study the deformation mechanism in wurtzite hexagonal structures. TEM results reveal that the prime deformation mechanism is slip on basal planes and in some cases, on pyramidal planes, and strain built up along particular directions. No evidence of phase transformation or cracking was observed in both materials. CL imaging reveals quenching of near band-edge emission by dislocations. In the second part, compositional inhomogeneity in quaternary GaInNAs and ternary InAlN alloys has been studied using TEM. It is shown that exposure to antimony during growth of GaInNAs results in uniform chemical composition in the epilayer, as antimony suppresses the surface mobility of adatoms that otherwise leads to two-dimensional growth and elemental segregation. In a separate study, compositional instability is observed in lattice-matched InAlN films grown on GaN, for growth beyond a certain thickness. Beyond 200 nm of thickness, two sub-layers with different indium content are observed, the top one with lower indium content.

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Date Created
  • 2013

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Optical and crystal structure characterizations of nanowires for infrared applications

Description

Semiconductor nanowires (NWs) are one dimensional materials and have size quantization effect when the diameter is sufficiently small. They can serve as optical wave guides along the length direction and

Semiconductor nanowires (NWs) are one dimensional materials and have size quantization effect when the diameter is sufficiently small. They can serve as optical wave guides along the length direction and contain optically active gain at the same time. Due to these unique properties, NWs are now very promising and extensively studied for nanoscale optoelectronic applications. A systematic and comprehensive optical and microstructural study of several important infrared semiconductor NWs is presented in this thesis, which includes InAs, PbS, InGaAs, erbium chloride silicate and erbium silicate. Micro-photoluminescence (PL) and transmission electron microscope (TEM) were utilized in conjunction to characterize the optical and microstructure of these wires. The focus of this thesis is on optical study of semiconductor NWs in the mid-infrared wavelengths. First, differently structured InAs NWs grown using various methods were characterized and compared. Three main PL peaks which are below, near and above InAs bandgap, respectively, were observed. The octadecylthiol self-assembled monolayer was employed to passivate the surface of InAs NWs to eliminate or reduce the effects of the surface states. The band-edge emission from wurtzite-structured NWs was completely recovered after passivatoin. The passivated NWs showed very good stability in air and under heat. In the second part, mid-infrared optical study was conducted on PbS wires of subwavelength diameter and lasing was demonstrated under optical pumping. The PbS wires were grown on Si substrate using chemical vapor deposition and have a rock-salt cubic structure. Single-mode lasing at the wavelength of ~3000-4000 nm was obtained from single as-grown PbS wire up to the temperature of 115 K. PL characterization was also utilized to demonstrate the highest crystallinity of the vertical arrays of InP and InGaAs/InP composition-graded heterostructure NWs made by a top-down fabrication method. TEM-related measurements were performed to study the crystal structures and elemental compositions of the Er-compound core-shell NWs. The core-shell NWs consist of an orthorhombic-structured erbium chloride silicate shell and a cubic-structured silicon core. These NWs provide unique Si-compatible materials with emission at 1530 nm for optical communications and solid state lasers.

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  • 2011

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Characterization of HgCdTe and related materials and substrates for third generation infrared detectors

Description

HgCdTe is currently the dominant material for infrared sensing and imaging, and is usually grown on lattice-matched bulk CdZnTe (CZT) substrates. There have been significant recent efforts to identify alternative

HgCdTe is currently the dominant material for infrared sensing and imaging, and is usually grown on lattice-matched bulk CdZnTe (CZT) substrates. There have been significant recent efforts to identify alternative substrates to CZT as well as alternative detector materials to HgCdTe. In this dissertation research, a wide range of transmission electron microscopy (TEM) imaging and analytical techniques was used in the characterization of epitaxial HgCdTe and related materials and substrates for third generation IR detectors. ZnTe layers grown on Si substrates are considered to be promising candidates for lattice-matched, large-area, and low-cost composite substrates for deposition of II-VI and III-V compound semiconductors with lattice constants near 6.1 Å. After optimizing MBE growth conditions including substrate pretreatment prior to film growth, as well as nucleation and growth temperatures, thick ZnTe/Si films with high crystallinity, low defect density, and excellent surface morphology were achieved. Changes in the Zn/Te flux ratio used during growth were also investigated. Small-probe microanalysis confirmed that a small amount of As was present at the ZnTe/Si interface. A microstructural study of HgCdTe/CdTe/GaAs (211)B and CdTe/GaAs (211)B heterostructures grown using MBE was carried out. High quality MBE-grown CdTe on GaAs(211)B substrates was demonstrated to be a viable composite substrate platform for HgCdTe growth. In addition, analysis of interfacial misfit dislocations and residual strain showed that the CdTe/GaAs interface was fully relaxed. In the case of HgCdTe/CdTe/ GaAs(211)B, thin HgTe buffer layers between HgCdTe and CdTe were also investigated for improving the HgCdTe crystal quality. A set of ZnTe layers epitaxially grown on GaSb(211)B substrates using MBE was studied using high resolution X-ray diffraction (HRXRD) measurements and TEM characterization in order to investigate conditions for defect-free growth. HRXRD results gave critical thickness estimates between 350 nm and 375 nm, in good agreement with theoretical predictions. Moreover, TEM results confirmed that ZnTe layers with thicknesses of 350 nm had highly coherent interfaces and very low dislocation densities, unlike samples with the thicker ZnTe layers.

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Date Created
  • 2012

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Transmission Electron Microscopy Characterization of Photovoltaic Semiconductor Materials

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The research of this dissertation has primarily involved using transmission electron microscopy (TEM) techniques to study several semiconductor materials considered promising for future photovoltaic device applications.

Layers of gallium phosphide (GaP)

The research of this dissertation has primarily involved using transmission electron microscopy (TEM) techniques to study several semiconductor materials considered promising for future photovoltaic device applications.

Layers of gallium phosphide (GaP) grown on silicon (Si) substrates were characterized by TEM and aberration-corrected scanning transmission electron microscopy (AC-STEM). High defect densities were observed for samples with GaP layer thicknesses 250nm and above. Anti-phase boundaries (APBs) within the GaP layers were observed at interfaces with the Si surfaces which were neither atomically flat nor abrupt, contradicting conventional understanding of APB formation.

Microcrystalline-Si (μc-Si) layers grown on crystalline-Si (c-Si) substrates were investigated. Without nanoparticle seeding, an undesired amorphous-Si (a-Si) layer grew below the μc-Si layer. With seeding, the undesired a-Si layer grew above the μc-Si layer, but μc-Si growth proceeded immediately at the c-Si surface. Ellipsometry measurements of percent crystallinity did not match TEM images, but qualitative agreement was found between TEM results and Ultraviolet Raman spectroscopy.

TEM and Xray spectroscopy were used to study metal-induced crystallization and layer exchange for aluminum/ germanium (Al/Ge). Only two samples definitively exhibited both Ge crystallization and layer exchange, and neither process was complete in either sample. The results were finally considered as inconclusive since no reliable path towards layer exchange and crystallization was established.

Plan-view TEM images of indium arsenide (InAs) quantum dots with gallium arsenide antimonide (GaAsSb) spacer layers revealed the termination of some threading dislocations in a sample with spacer-layer thicknesses of 2nm, while a sample with 15-nm-thick spacer layers showed a dense, cross-hatched pattern. Cross-sectional TEM images of samples with 5-nm and 10-nm spacer-layer thicknesses showed less layer undulation in the latter sample. These observations supported photoluminescence (PL) and Xray diffraction (XRD) results, which indicated that GaAsSb spacer layers with 10-nm thickness yielded the highest quality material for photovoltaic device applications.

a-Si/c-Si samples treated by hydrogen plasma were investigated using high-resolution TEM. No obvious structural differences were observed that would account for the large differences measured in minority carrier lifetimes. This key result suggested that other factors such as point defects, hydrogen content, or interface charge must be affecting the lifetimes.

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Date Created
  • 2020

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Nanoscale heterogeneities in visible light absorbing photocatalysts: connecting structure to functionality through electron microscopy and spectroscopy

Description

Photocatalytic water splitting over suspended nanoparticles represents a potential solution for achieving CO2-neutral energy generation and storage. To design efficient photocatalysts, a fundamental understanding of the material’s structure, electronic properties,

Photocatalytic water splitting over suspended nanoparticles represents a potential solution for achieving CO2-neutral energy generation and storage. To design efficient photocatalysts, a fundamental understanding of the material’s structure, electronic properties, defects, and how these are controlled via synthesis is essential. Both bulk and nanoscale materials characterization, in addition to various performance metrics, can be combined to elucidate functionality at multiple length scales. In this work, two promising visible light harvesting systems are studied in detail: Pt-functionalized graphitic carbon nitrides (g-CNxHys) and TiO2-supported CeO2-x composites.

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.

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Date Created
  • 2019

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Characterization of oxide thin films and interfaces using transmission electron microscopy

Description

Multifunctional oxide thin-films grown on silicon and several oxide substrates have been characterized using High Resolution (Scanning) Transmission Electron Microscopy (HRTEM), Energy-Dispersive X-ray Spectroscopy (EDX), and Electron Energy-Loss Spectroscopy (EELS).

Multifunctional oxide thin-films grown on silicon and several oxide substrates have been characterized using High Resolution (Scanning) Transmission Electron Microscopy (HRTEM), Energy-Dispersive X-ray Spectroscopy (EDX), and Electron Energy-Loss Spectroscopy (EELS). Oxide thin films grown on SrTiO3/Si pseudo-substrate showed the presence of amorphised SrTiO3 (STO) at the STO/Si interface. Oxide/oxide interfaces were observed to be atomically clean with very few defects.

Al-doped SrTiO3 thin films grown on Si were of high crystalline quality. The Ti/O ratio estimated from EELS line scans revealed that substitution of Ti by Al created associated O vacancies. The strength of the crystal field in STO was measured using EELS, and decreased by ~1.0 eV as Ti4+ was substituted by Al3+. The damping of O-K EELS peaks confirmed the rise in oxygen vacancies. For Co-substituted STO films grown on Si, the EDS and EELS spectra across samples showed Co doping was quite random. The substitution of Ti4+ with Co3+ or Co2+ created associated oxygen vacancies for charge balance. Presence of oxygen vacancies was also confirmed by shift of Ti-L EELS peaks towards lower energy by ~0.4 eV. The crystal-field strength decreased by ~0.6 eV as Ti4+ was partially substituted by Co3+ or Co2+.

Spinel Co3O4 thin films grown on MgAl2O4 (110) were observed to have excellent crystalline quality. The structure of the Co3O4/MgAl2O4 interface was determined using HRTEM and image simulations. It was found that MgAl2O4 substrate is terminated with Al and oxygen. Stacking faults and associated strain fields in spinel Co3O4 were found along [111], [001], and [113] using Geometrical Phase Analysis.

NbO2 films on STO (111) were observed to be tetragonal with lattice parameter of 13.8 Å and NbO films on LSAT (111) were observed to be cubic with lattice parameter of 4.26 Å. HRTEM showed formation of high quality NbOx films and excellent coherent interface. HRTEM of SrAl4 on LAO (001) confirmed an island growth mode. The SrAl4 islands were highly crystalline with excellent epitaxial registry with LAO. By comparing HRTEM images with image simulations, the interface structure was determined to consist of Sr-terminated SrAl4 (001) on AlO2-terminated LAO (001).

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Date Created
  • 2015

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Atomic level study of structural changes of TiO2 based photocatalysts during solar water splitting reactions using TEM

Description

Photocatalytic water splitting is a promising technique to produce H2 fuels from water using sustainable solar energy. To better design photocatalysts, the understanding of charge transfer at surfaces/interfaces and the

Photocatalytic water splitting is a promising technique to produce H2 fuels from water using sustainable solar energy. To better design photocatalysts, the understanding of charge transfer at surfaces/interfaces and the corresponding structure change during the reaction is very important. Local structural and chemical information on nanoparticle surfaces or interfaces can be achieved through characterizations on transmission electron microscopy (TEM). Emphasis should be put on materials structure changes during the reactions in their “working conditions”. Environmental TEM with in situ light illumination system allows the photocatalysts to be studied under light irradiation when exposed to H2O vapor. A set of ex situ and in situ TEM characterizations are carried out on typical types of TiO2 based photocatalysts. The observed structure changes during the reaction are correlated with the H2 production rate for structure-property relationships.

A surface disordering was observed in situ when well-defined anatase TiO2 rhombohedral nanoparticles were exposed to 1 Torr H2O vapor and 10suns light inside the environmental TEM. The disordering is believed to be related to high density of hydroxyl groups formed on surface oxygen vacancies during water splitting reactions.

Pt co-catalyst on TiO2 is able to split pure water producing H2 and O2. The H2 production rate drops during the reaction. Particle size growth during reaction was discovered with Z-contrast images. The particle size growth is believed to be a photo-electro-chemical Ostwald ripening.

Characterizations were also carried out on a more complicated photocatalyst system: Ni/NiO core/shell co-catalyst on TiO2. A decrease of the H2 production rate resulting from photo-corrosion was observed. The Ni is believed to be oxidized to Ni2+ by OH• radicals which are intermediate products of H2O oxidation. The mechanism that the OH• radicals leak into the cores through cracks on NiO shells is more supported by experiments.

Overall this research has done a comprehensive ex situ and in situ TEM characterizations following some typical TiO2 based photocatalysts during reactions. This research has shown the technique availability to study photocatalyst inside TEM in photocatalytic conditions. It also demonstrates the importance to follow structure changes of materials during reactions in understanding deactivation mechanisms.

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  • 2015

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Fluctuation electron microscopy of amorphous and polycrystalline materials

Description

Fluctuation Electron Microscopy (FEM) has become an effective materials' structure characterization technique, capable of probing medium-range order (MRO) that may be present in amorphous materials. Although its sensitivity to MRO

Fluctuation Electron Microscopy (FEM) has become an effective materials' structure characterization technique, capable of probing medium-range order (MRO) that may be present in amorphous materials. Although its sensitivity to MRO has been exercised in numerous studies, FEM is not yet a quantitative technique. The holdup has been the discrepancy between the computed kinematical variance and the experimental variance, which previously was attributed to source incoherence. Although high-brightness, high coherence, electron guns are now routinely available in modern electron microscopes, they have not eliminated this discrepancy between theory and experiment. The main objective of this thesis was to explore, and to reveal, the reasons behind this conundrum.

The study was started with an analysis of the speckle statistics of tilted dark-field TEM images obtained from an amorphous carbon sample, which confirmed that the structural ordering is sensitively detected by FEM. This analysis also revealed the inconsistency between predictions of the source incoherence model and the experimentally observed variance.

FEM of amorphous carbon, amorphous silicon and ultra nanocrystalline diamond samples was carried out in an attempt to explore the conundrum. Electron probe and sample parameters were varied to observe the scattering intensity variance behavior. Results were compared to models of probe incoherence, diffuse scattering, atom displacement damage, energy loss events and multiple scattering. Models of displacement decoherence matched the experimental results best.

Decoherence was also explored by an interferometric diffraction method using bilayer amorphous samples, and results are consistent with strong displacement decoherence in addition to temporal decoherence arising from the electron source energy spread and energy loss events in thick samples.

It is clear that decoherence plays an important role in the long-standing discrepancy between experimental FEM and its theoretical predictions.

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Date Created
  • 2015

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Atomic-level analysis of oxygen exchange reactions on ceria-based catalysts

Description

Non-stoichiometric oxides play a critical role in many catalytic, energy, and sensing technologies, providing the ability to reversibly exchange oxygen with the ambient environment through the creation and annihilation of

Non-stoichiometric oxides play a critical role in many catalytic, energy, and sensing technologies, providing the ability to reversibly exchange oxygen with the ambient environment through the creation and annihilation of surface oxygen vacancies. Oxygen exchange at the surfaces of these materials is strongly influenced by atomic structure, which varies significantly across nanoparticle surfaces. The studies presented herein elucidate the relationship between surface structure behaviors and oxygen exchange reactions on ceria (CeO2) catalyst materials. In situ aberration-corrected transmission electron microscopy (AC-TEM) techniques were developed and employed to correlate dynamic atomic-level structural heterogeneities to local oxygen vacancy activity.

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.

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Date Created
  • 2019