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- Creators: Liu, Jingyue
Description
The research described in this dissertation involved the use of transmission electron microscopy (TEM) to characterize II-VI and III-V compound semiconductor quantum dots (QDs) and dilute-nitride alloys grown by molecular beam epitaxy (MBE) and intended for photovoltaic applications. The morphology of CdTe QDs prepared by the post-annealing MBE method were characterized by various microscopy techniques including high-resolution transmission electron microscopy (HR-TEM), and high-angle annular-dark-field scanning transmission electron microscopy (HAADF-STEM). Extensive observations revealed that the of QD shapes were not well-defined, and the QD size and spatial distribution were not determined by the amount of CdTe deposition. These results indicated that the formation of II-VI QDs using a post-annealing treatment did not follow the conventional growth mechanism for III-V and IV-IV materials. The structural properties of dilute-nitride GaAsNx films grown using plasma-assisted MBE were characterized by TEM and HAADF-STEM. A significant amount of the nitrogen incorporated into the dilute nitride films was found to be interstitial, and that fluctuations in local nitrogen composition also occurred during growth. Post-growth partial relaxation of strain resulted in the formation of {110}-oriented microcracks in the sample with the largest substitutional nitrogen composition. Single- and multi-layered InAs QDs grown on GaAsSb/GaAs composite substrates were investigated using HR-TEM and HAADF-STEM. Correlation between the structural and optoelectronic properties revealed that the GaAsSb barrier layers had played an important role in tuning the energy-band alignments but without affecting the overall structural morphology. However, according to both XRD measurement and electron microscopy the densities of dislocations increased as the number of QD layers built up. An investigation of near-wetting layer-free InAs QDs incorporated with AlAs/GaAs spacer layers was carried out. The microscopy observations revealed that both embedded and non-embedded near-wetting layer-free InAs QDs did not have well-defined shapes unlike conventional InAs QDs. According to AFM analysis and plan-view TEM characterization, the InAs QDs incorporated with spacer layers had smaller dot density and more symmetrical larger sizes with an apparent bimodal size distribution (two distinct families of large and small dots) in comparison with conventional InAs QDs grown without any spacer layer.
ContributorsTang, Dinghao (Author) / Smith, David J. (Thesis advisor) / Crozier, Peter A. (Committee member) / Liu, Jingyue (Committee member) / Mccartney, Martha R (Committee member) / Arizona State University (Publisher)
Created2014
Description
This honors thesis is focused on two separate catalysis projects conducted under the mentorship of Dr. Javier Pérez-Ramírez at ETH Zürich. The first project explored ethylene oxychlorination over supported europium oxychloride catalysts. The second project investigated alkyne semihydrogenation over nickel phosphide catalysts. This work is the subject of a publication of which I am a co-author, as cited below.
Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.
Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.
This work is the subject of a publication of which I am a co-author, as cited below.
D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430
Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.
Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.
This work is the subject of a publication of which I am a co-author, as cited below.
D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430
ContributorsTata, Bharath (Author) / Deng, Shuguang (Thesis director) / Muhich, Christopher (Committee member) / Chemical Engineering Program (Contributor, Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
Description
Operando transmission electron microscopy (TEM) is an extension of in-situ TEM in which the performance of the material being observed is measured simultaneously. This is of great value, since structure-performance relationships lie at the heart of materials science. For catalyst materials, like the SiO2-supported Ru nanoparticles studied, the important performance metric, catalyst activity, is measured inside the microscope by determining the gas composition during imaging. This is accomplished by acquisition of electron energy loss spectra (EELS) of the gas in the environmental TEM while catalysis is taking place. In this work, automated methods for rapidly quantifying low-loss and core-loss EELS of gases were developed. A new sample preparation method was also established to increase catalytic conversion inside a differentially-pumped environmental TEM, and the maximum CO conversion observed was about 80%. A system for mixing gases and delivering them to the environmental TEM was designed and built, and a method for locating and imaging nanoparticles in zone axis orientations while minimizing electron dose rate was determined.
After atomic resolution images of Ru nanoparticles observed during CO oxidation were obtained, the shape and surface structures of these particles was investigated. A Wulff model structure for Ru particles was compared to experimental images both by manually rotating the model, and by automatically determining a matching orientation using cross-correlation of shape signatures. From this analysis, it was determined that most Ru particles are close to Wulff-shaped during CO oxidation. While thick oxide layers were not observed to form on Ru during CO oxidation, thin RuO2 layers on the surface of Ru nanoparticles were imaged with atomic resolution for the first time. The activity of these layers is discussed in the context of the literature on the subject, which has thus far been inconclusive. We conclude that disordered oxidized ruthenium, rather than crystalline RuO2 is the most active species.
After atomic resolution images of Ru nanoparticles observed during CO oxidation were obtained, the shape and surface structures of these particles was investigated. A Wulff model structure for Ru particles was compared to experimental images both by manually rotating the model, and by automatically determining a matching orientation using cross-correlation of shape signatures. From this analysis, it was determined that most Ru particles are close to Wulff-shaped during CO oxidation. While thick oxide layers were not observed to form on Ru during CO oxidation, thin RuO2 layers on the surface of Ru nanoparticles were imaged with atomic resolution for the first time. The activity of these layers is discussed in the context of the literature on the subject, which has thus far been inconclusive. We conclude that disordered oxidized ruthenium, rather than crystalline RuO2 is the most active species.
ContributorsMiller, Benjamin (Author) / Crozier, Peter (Thesis advisor) / Liu, Jingyue (Committee member) / McCartney, Martha (Committee member) / Rez, Peter (Committee member) / Arizona State University (Publisher)
Created2016
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 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.
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.
ContributorsLawrence, Ethan Lee (Author) / Crozier, Peter A. (Thesis advisor) / Lin, Jerry (Committee member) / Liu, Jingyue (Committee member) / Petuskey, William (Committee member) / Arizona State University (Publisher)
Created2019
Description
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.
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.
ContributorsBoley, Allison (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha R. (Thesis advisor) / Liu, Jingyue (Committee member) / Bennett, Peter (Committee member) / Arizona State University (Publisher)
Created2020