Matching Items (5)
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- All Subjects: Thin films
- All Subjects: Catalysis
- Creators: Bertoni, Mariana
Description
Carrier lifetime is one of the few parameters which can give information about the low defect densities in today's semiconductors. In principle there is no lower limit to the defect density determined by lifetime measurements. No other technique can easily detect defect densities as low as 10-9 - 10-10 cm-3 in a simple, contactless room temperature measurement. However in practice, recombination lifetime τr measurements such as photoconductance decay (PCD) and surface photovoltage (SPV) that are widely used for characterization of bulk wafers face serious limitations when applied to thin epitaxial layers, where the layer thickness is smaller than the minority carrier diffusion length Ln. Other methods such as microwave photoconductance decay (µ-PCD), photoluminescence (PL), and frequency-dependent SPV, where the generated excess carriers are confined to the epitaxial layer width by using short excitation wavelengths, require complicated configuration and extensive surface passivation processes that make them time-consuming and not suitable for process screening purposes. Generation lifetime τg, typically measured with pulsed MOS capacitors (MOS-C) as test structures, has been shown to be an eminently suitable technique for characterization of thin epitaxial layers. It is for these reasons that the IC community, largely concerned with unipolar MOS devices, uses lifetime measurements as a "process cleanliness monitor." However when dealing with ultraclean epitaxial wafers, the classic MOS-C technique measures an effective generation lifetime τg eff which is dominated by the surface generation and hence cannot be used for screening impurity densities. I have developed a modified pulsed MOS technique for measuring generation lifetime in ultraclean thin p/p+ epitaxial layers which can be used to detect metallic impurities with densities as low as 10-10 cm-3. The widely used classic version has been shown to be unable to effectively detect such low impurity densities due to the domination of surface generation; whereas, the modified version can be used suitably as a metallic impurity density monitoring tool for such cases.
ContributorsElhami Khorasani, Arash (Author) / Alford, Terry (Thesis advisor) / Goryll, Michael (Committee member) / Bertoni, Mariana (Committee member) / Arizona State University (Publisher)
Created2013
Description
A series of pyrite thin films were synthesized using a novel sequential evaporation
technique to study the effects of substrate temperature on deposition rate and micro-structure of
the deposited material. Pyrite was deposited in a monolayer-by-monolayer fashion using
sequential evaporation of Fe under high vacuum, followed by sulfidation at high S pressures
(typically > 1 mTorr to 1 Torr). Thin films were synthesized using two different growth processes; a
one-step process in which a constant growth temperature is maintained throughout growth, and a
three-step process in which an initial low temperature seed layer is deposited, followed by a high
temperature layer, and then finished with a low temperature capping layer. Analysis methods to
analyze the properties of the films included Glancing Angle X-Ray Diffraction (GAXRD),
Rutherford Back-scattering Spectroscopy (RBS), Transmission Electron Microscopy (TEM),
Secondary Ion Mass Spectroscopy (SIMS), 2-point IV measurements, and Hall effect
measurements. Our results show that crystallinity of the pyrite thin film improves and grain size
increases with increasing substrate temperature. The sticking coefficient of Fe was found to
increase with increasing growth temperature, indicating that the Fe incorporation into the growing
film is a thermally activated process.
technique to study the effects of substrate temperature on deposition rate and micro-structure of
the deposited material. Pyrite was deposited in a monolayer-by-monolayer fashion using
sequential evaporation of Fe under high vacuum, followed by sulfidation at high S pressures
(typically > 1 mTorr to 1 Torr). Thin films were synthesized using two different growth processes; a
one-step process in which a constant growth temperature is maintained throughout growth, and a
three-step process in which an initial low temperature seed layer is deposited, followed by a high
temperature layer, and then finished with a low temperature capping layer. Analysis methods to
analyze the properties of the films included Glancing Angle X-Ray Diffraction (GAXRD),
Rutherford Back-scattering Spectroscopy (RBS), Transmission Electron Microscopy (TEM),
Secondary Ion Mass Spectroscopy (SIMS), 2-point IV measurements, and Hall effect
measurements. Our results show that crystallinity of the pyrite thin film improves and grain size
increases with increasing substrate temperature. The sticking coefficient of Fe was found to
increase with increasing growth temperature, indicating that the Fe incorporation into the growing
film is a thermally activated process.
ContributorsWertheim, Alex (Author) / Newman, Nathan (Thesis advisor) / Singh, Rakesh (Committee member) / Bertoni, Mariana (Committee member) / Arizona State University (Publisher)
Created2014
Description
The purpose of this thesis was to investigate the properties of amorphous and crystalline NaTaO3 to determine what makes amorphous NaTaO3 a suitable photocatalyst for water splitting applications. Amorphous and nanocrystalline NaTaO3 were synthesized and characterized using X-Ray Diffraction (XRD), Raman Spectroscopy, and Fourier Transform Infrared Spectroscopy (FT-IR). The photocatalytic activity of the materials was analyzed using methylene blue degradation as an indicator of photocatalytic activity. The amorphous material showed significant photocatalytic activity in methylene blue degradation experiments, removing 100% of a 0.1 mmol methylene blue solution in 20 minutes, compared to the monoclinic crystalline NaTaO3, which showed negligible photocatalytic activity. Additional electrochemical characterization studies were carried out with methyl viologen (MV2+) to determine the band structure of the materials. Performing these synthesis and characterization has provided insight into further investigation of amorphous NaTaO3 and what makes the material an effective and inexpensive photocatalyst.
ContributorsRorrer, Julie Elaine (Author) / Chan, Candace (Thesis director) / Bertoni, Mariana (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05
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
Polycrystalline CdS/CdTe solar cells continue to dominate the thin-film photovoltaics industry with an achieved record efficiency of over 22% demonstrated by First Solar, yet monocrystalline CdTe devices have received considerably less attention over the years. Monocrystalline CdTe double-heterostructure solar cells show great promise with respect to addressing the problem of low Voc with the passing of the 1 V benchmark. Rapid progress has been made in driving the efficiency in these devices ever closer to the record presently held by polycrystalline thin-films. This achievement is primarily due to the utilization of a remote p-n heterojunction in which the heavily doped contact materials, which are so problematic in terms of increasing non-radiative recombination inside the absorber, are moved outside of the CdTe double heterostructure with two MgyCd1-yTe barrier layers to provide confinement and passivation at the CdTe surfaces. Using this design, the pursuit and demonstration of efficiencies beyond 20% in CdTe solar cells is reported through the study and optimization of the structure barriers, contacts layers, and optical design. Further development of a wider bandgap MgxCd1-xTe solar cell based on the same design is included with the intention of applying this knowledge to the development of a tandem solar cell constructed on a silicon subcell. The exploration of different hole-contact materials—ZnTe, CuZnS, and a-Si:H—and their optimization is presented throughout the work. Devices utilizing a-Si:H hole contacts exhibit open-circuit voltages of up to 1.11 V, a maximum total-area efficiency of 18.5% measured under AM1.5G, and an active-area efficiency of 20.3% for CdTe absorber based devices. The achievement of voltages beyond 1.1V while still maintaining relatively high fill factors with no rollover, either before or after open-circuit, is a promising indicator that this approach can result in devices surpassing the 22% record set by polycrystalline designs. MgxCd1-xTe absorber based devices have been demonstrated with open-circuit voltages of up to 1.176 V and a maximum active-area efficiency of 11.2%. A discussion of the various loss mechanisms present within these devices, both optical and electrical, concludes with the presentation of a series of potential design changes meant to address these issues.
ContributorsBecker, Jacob J (Author) / Zhang, Yong-Hang (Thesis advisor) / Bertoni, Mariana (Committee member) / Vasileska, Dragica (Committee member) / Johnson, Shane (Committee member) / Arizona State University (Publisher)
Created2017