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- All Subjects: tem
- Creators: Ponce, Fernando
Description
Group III-nitride semiconductors have been commercially used in the fabrication of light-emitting diodes and laser diodes, covering the ultraviolet-visible-infrared spectral range and exhibit unique properties suitable for modern optoelectronic applications. InGaN ternary alloys have energy band gaps ranging from 0.7 to 3.4 eV. It has a great potential in the application for high efficient solar cells. AlGaN ternary alloys have energy band gaps ranging from 3.4 to 6.2 eV. These alloys have a great potential in the application of deep ultra violet laser diodes. However, there are still many issues with these materials that remain to be solved. In this dissertation, several issues concerning structural, electronic, and optical properties of III-nitrides have been investigated using transmission electron microscopy. First, the microstructure of InxGa1-xN (x = 0.22, 0.46, 0.60, and 0.67) films grown by metal-modulated epitaxy on GaN buffer /sapphire substrates is studied. The effect of indium composition on the structure of InGaN films and strain relaxation is carefully analyzed. High luminescence intensity, low defect density, and uniform full misfit strain relaxation are observed for x = 0.67. Second, the properties of high-indium-content InGaN thin films using a new molecular beam epitaxy method have been studied for applications in solar cell technologies. This method uses a high quality AlN buffer with large lattice mismatch that results in a critical thickness below one lattice parameter. Finally, the effect of different substrates and number of gallium sources on the microstructure of AlGaN-based deep ultraviolet laser has been studied. It is found that defects in epitaxial layer are greatly reduced when the structure is deposited on a single crystal AlN substrate. Two gallium sources in the growth of multiple quantum wells active region are found to cause a significant improvement in the quality of quantum well structures.
ContributorsWei, Yong (Author) / Ponce, Fernando (Thesis advisor) / Chizmeshya, Andrew (Committee member) / McCartney, Martha (Committee member) / Menéndez, Jose (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2014
Description
The research described in this dissertation has involved the use of transmission electron microcopy (TEM) to characterize the structural properties of II-VI and III-V compound semiconductor heterostructures and superlattices. The microstructure of thick ZnTe epilayers (~2.4 µm) grown by molecular beam epitaxy (MBE) under virtually identical conditions on GaSb, InAs, InP and GaAs (100) substrates were compared using TEM. High-resolution electron micrographs revealed a highly coherent interface for the ZnTe/GaSb sample, and showed extensive areas with well-separated interfacial misfit dislocations for the ZnTe/InAs sample. Lomer edge dislocations and 60o dislocations were commonly observed at the interfaces of the ZnTe/InP and ZnTe/GaAs samples. The amount of residual strain at the interfaces was estimated to be 0.01% for the ZnTe/InP sample and -0.09% for the ZnTe/GaAs sample. Strong PL spectra for all ZnTe samples were observed from 80 to 300 K. High quality GaSb grown by MBE on ZnTe/GaSb (001) virtual substrates with a temperature ramp at the beginning of the GaSb growth has been demonstrated. High-resolution X-ray diffraction (XRD) showed clear Pendellösung thickness fringes from both GaSb and ZnTe epilayers. Cross-section TEM images showed excellent crystallinity and smooth morphology for both ZnTe/GaSb and GaSb/ZnTe interfaces. Plan-view TEM image revealed the presence of Lomer dislocations at the interfaces and threading dislocations in the top GaSb layer. The defect density was estimated to be ~1 x107/cm2. The PL spectra showed improved optical properties when using the GaSb transition layer grown on ZnTe with a temperature ramp. The structural properties of strain-balanced InAs/InAs1-xSbx SLs grown on GaSb (001) substrates by metalorganic chemical vapor deposition (MOCVD) and MBE, have been studied using XRD and TEM. Excellent structural quality of the InAs/InAs1-xSbx SLs grown by MOCVD has been demonstrated. Well-defined ordered-alloy structures within individual InAs1-xSbx layers were observed for samples grown by modulated MBE. However, the ordering disappeared when defects propagating through the SL layers appeared during growth. For samples grown by conventional MBE, high-resolution images revealed that interfaces for InAs1-xSbx grown on InAs layers were sharper than for InAs grown on InAs1-xSbx layers, most likely due to a Sb surfactant segregation effect.
ContributorsOuyang, Lu (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha (Committee member) / Ponce, Fernando (Committee member) / Chamberlin, Ralph (Committee member) / Menéndez, Jose (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
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). 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).
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).
ContributorsDhamdhere, Ajit (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha R. (Committee member) / Chamberlin, Ralph (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2015