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- All Subjects: Interface
- Creators: Smith, David
Description
In this dissertation, the interface chemistry and electronic structure of plasma-enhanced atomic layer deposited (PEALD) dielectrics on GaN are investigated with x-ray and ultraviolet photoemission spectroscopy (XPS and UPS). Three interrelated issues are discussed in this study: (1) PEALD dielectric growth process optimization, (2) interface electronic structure of comparative PEALD dielectrics on GaN, and (3) interface electronic structure of PEALD dielectrics on Ga- and N-face GaN. The first study involved an in-depth case study of PEALD Al2O3 growth using dimethylaluminum isopropoxide, with a special focus on oxygen plasma effects. Saturated and self-limiting growth of Al2O3 films were obtained with an enhanced growth rate within the PEALD temperature window (25-220 ºC). The properties of Al2O3 deposited at various temperatures were characterized to better understand the relation between the growth parameters and film properties. In the second study, the interface electronic structures of PEALD dielectrics on Ga-face GaN films were measured. Five promising dielectrics (Al2O3, HfO2, SiO2, La2O3, and ZnO) with a range of band gap energies were chosen. Prior to dielectric growth, a combined wet chemical and in-situ H2/N2 plasma clean process was employed to remove the carbon contamination and prepare the surface for dielectric deposition. The surface band bending and band offsets were measured by XPS and UPS for dielectrics on GaN. The trends of the experimental band offsets on GaN were related to the dielectric band gap energies. In addition, the experimental band offsets were near the calculated values based on the charge neutrality level model. The third study focused on the effect of the polarization bound charge of the Ga- and N-face GaN on interface electronic structures. A surface pretreatment process consisting of a NH4OH wet chemical and an in-situ NH3 plasma treatment was applied to remove carbon contamination, retain monolayer oxygen coverage, and potentially passivate N-vacancy related defects. The surface band bending and polarization charge compensation of Ga- and N-face GaN were investigated. The surface band bending and band offsets were determined for Al2O3, HfO2, and SiO2 on Ga- and N-face GaN. Different dielectric thicknesses and post deposition processing were investigated to understand process related defect formation and/or reduction.
ContributorsYang, Jialing (Author) / Nemanich, Robert J (Thesis advisor) / Chen, Tingyong (Committee member) / Peng, Xihong (Committee member) / Ponce, Fernando (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2014
Description
In this dissertation, in-situ X-ray and ultraviolet photoemission spectroscopy have been employed to study the interface chemistry and electronic structure of potential high-k gate stack materials. In these gate stack materials, HfO2 and La2O3 are selected as high-k dielectrics, VO2 and ZnO serve as potential channel layer materials. The gate stack structures have been prepared using a reactive electron beam system and a plasma enhanced atomic layer deposition system. Three interrelated issues represent the central themes of the research: 1) the interface band alignment, 2) candidate high-k materials, and 3) band bending, internal electric fields, and charge transfer. 1) The most highlighted issue is the band alignment of specific high-k structures. Band alignment relationships were deduced by analysis of XPS and UPS spectra for three different structures: a) HfO2/VO2/SiO2/Si, b) HfO2-La2O3/ZnO/SiO2/Si, and c) HfO2/VO2/ HfO2/SiO2/Si. The valence band offset of HfO2/VO2, ZnO/SiO2 and HfO2/SiO2 are determined to be 3.4 ± 0.1, 1.5 ± 0.1, and 0.7 ± 0.1 eV. The valence band offset between HfO2-La2O3 and ZnO was almost negligible. Two band alignment models, the electron affinity model and the charge neutrality level model, are discussed. The results show the charge neutrality model is preferred to describe these structures. 2) High-k candidate materials were studied through comparison of pure Hf oxide, pure La oxide, and alloyed Hf-La oxide films. An issue with the application of pure HfO2 is crystallization which may increase the leakage current in gate stack structures. An issue with the application of pure La2O3 is the presence of carbon contamination in the film. Our study shows that the alloyed Hf-La oxide films exhibit an amorphous structure along with reduced carbon contamination. 3) Band bending and internal electric fields in the gate stack structure were observed by XPS and UPS and indicate the charge transfer during the growth and process. The oxygen plasma may induce excess oxygen species with negative charges, which could be removed by He plasma treatment. The final HfO2 capping layer deposition may reduce the internal potential inside the structures. The band structure was approaching to a flat band condition.
ContributorsZhu, Chiyu (Author) / Nemanich, Robert (Thesis advisor) / Chamberlin, Ralph (Committee member) / Chen, Tingyong (Committee member) / Ponce, Fernando (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2012
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 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.
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.
ContributorsZhang, Liuxian (Author) / Crozier, Peter (Thesis advisor) / Smith, David (Committee member) / Chan, Candace (Committee member) / Liu, Jingyue (Committee member) / Arizona State University (Publisher)
Created2015