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- All Subjects: Physics
- Creators: Rez, Peter
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 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.
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.
ContributorsRezikyan, Aram (Author) / Treacy, Michael M.J. (Thesis advisor) / Smith, David J. (Committee member) / McCartney, Martha R. (Committee member) / Rez, Peter (Committee member) / Arizona State University (Publisher)
Created2015
Raman spectroscopy characterization of anharmonicity and alloying effects in semiconductor materials
Description
The chemical sensitivity and spatial resolution of Raman spectroscopy, combined with the sensitivity of modern systems that can easily detect single atomic layers, have made this technique a preferred choice for the strain characterization of complex systems such as nanoscale complementary metal-oxide-semiconductor - CMOS - devices. A disadvantage of Raman spectroscopy, however, is that the shifts associated with strain are not related to the geometrical deformations in any obvious way, so that careful calibrations are needed to determine the anharmonic coefficients (p, q and r) that relate strain to Raman shifts. A new set of measurements of the Raman shift in strained Ge films grown on relaxed SiGe buffer layers deposited on Si substrates is presented, and thereby, a new consistent set of values for the parameters p and q for Ge has been proposed. In this dissertation the study of the vibrational properties of Ge1-xSnx alloys has also been reported. The temperature dependence of the Raman spectrum of Ge-rich Ge1-x Snx and Ge1-x-ySi xSny alloys has been determined in the 10 K - 450 K range. The Raman line shift and width changes as a function of temperature are found to be virtually identical to those observed in bulk Ge. This result shows that the anharmonic decay process responsible for the temperature dependence is extremely robust against the alloy perturbation.
ContributorsBagchi, Sampriti (Author) / Menéndez, Jose (Thesis advisor) / Treacy, Michael (Committee member) / Ponce, Fernando (Committee member) / Tsen, Kong-Thon (Committee member) / Rez, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
In this work, a new method, "Nanobonding" [1,2] is conceived and researched to bond Si-based surfaces, via nucleation and growth of a 2 D silicon oxide SiOxHx interphase connecting the surfaces at the nanoscale across macroscopic domains. Nanobonding cross-bridges two smooth surfaces put into mechanical contact in an O2/H2O mixed ambient below T <200 °C via arrays of SiOxHx molecules connecting into a continuous macroscopic bonding interphase. Nano-scale surface planarization via wet chemical processing and new spin technology are compared via Tapping Mode Atomic Force Microscopy (TMAFM) , before and after nano-bonding. Nanobonding uses precursor phases, 2D nano-films of beta-cristobalite (beta-c) SiO2, nucleated on Si(100) via the Herbots-Atluri (H-A) method [1]. beta-c SiO2 on Si(100) is ordered and flat with atomic terraces over 20 nm wide, well above 2 nm found in native oxides. When contacted with SiO2 this ultra-smooth nanophase can nucleate and grow domains with cross-bridging molecular strands of hydroxylated SiOx, instead of point contacts. The high density of molecular bonds across extended terraces forms a strong bond between Si-based substrates, nano- bonding [2] the Si and silica. A new model of beta-cristobalite SiO2 with its <110> axis aligned along Si[100] direction is simulated via ab-initio methods in a nano-bonded stack with beta-c SiO2 in contact with amorphous SiO2 (a-SiO2), modelling cross-bridging molecular bonds between beta-c SiO2 on Si(100) and a-SiO2 as during nanobonding. Computed total energies are compared with those found for Si(100) and a-SiO2 and show that the presence of two lattice cells of !-c SiO2 on Si(100) and a-SiO2 lowers energy when compared to Si(100)/ a-SiO2 Shadow cone calculations on three models of beta-c SiO2 on Si(100) are compared with Ion Beam Analysis of H-A processed Si(100). Total surface energy measurements via 3 liquid contact angle analysis of Si(100) after H-A method processing are also compared. By combining nanobonding experiments, TMAFM results, surface energy data, and ab-initio calculations, an atomistic model is derived and nanobonding is optimized. [1] US Patent 6,613,677 (9/2/03), 7,851,365 (12/14/10), [2] Patent Filed: 4/30/09, 10/1/2011
ContributorsWhaley, Shawn D (Author) / Culbertson, Robert J. (Thesis advisor) / Herbots, Nicole (Committee member) / Rez, Peter (Committee member) / Marzke, Robert F (Committee member) / Lindsay, Stuart (Committee member) / Chamberlin, Ralph V (Committee member) / Arizona State University (Publisher)
Created2011
Description
Many species e.g. sea urchin form amorphous calcium carbonate (ACC) precursor phases that subsequently transform into crystalline CaCO3. It is certainly possible that the biogenic ACC might have more than 10 wt% Mg and ∼ 3 wt% of water. The structure of ACC and the mechanisms by which it transforms to crystalline phase are still poorly understood. In this dissertation our goal is to determine an atomic structure model that is consistent with diffraction and IR measurements of ACC. For this purpose a calcite supercell with 24 formula units, containing 120 atoms, was constructed. Various configurations with substitution of Ca by 6 Mg ions (6 wt.%) and insertion of 3-5 H2O molecules (2.25-3.75 wt.%) in the interstitial positions of the supercell, were relaxed using a robust density function code VASP. The most noticeable effects were the tilts of CO3 groups and the distortion of Ca sub-lattice, especially in the hydrated case. The distributions of Ca-Ca nearest neighbor distance and CO3 tilts were extracted from various configurations. The same methods were also applied to aragonite. Sampling from the calculated distortion distributions, we built models for amorphous calcite/aragonite of size ∼ 1700 nm3 based on a multi-scale modeling scheme. We used these models to generate diffraction patterns and profiles with our diffraction code. We found that the induced distortions were not enough to generate a diffraction profile typical of an amorphous material. We then studied the diffraction profiles from several nano-crystallites as recent studies suggest that ACC might be a random array of nanocryatallites. It was found that the generated diffraction profile from a nano-crystallite of size ∼ 2 nm3 is similar to that from the ACC.
ContributorsSinha, Sourabh (Author) / Rez, Peter (Thesis advisor) / Bearat, Hamdallah A. (Committee member) / Bennett, Peter A. (Committee member) / McCartney, Martha R. (Committee member) / Peng, Xihong (Committee member) / Arizona State University (Publisher)
Created2012
Description
In this dissertation, various characterization techniques have been used to investigate many aspects of the properties of III-nitride materials and devices for optoelectronic applications.
The first part of this work is focused on the evolution of microstructures of BAlN thin films. The films were grown by flow-modulated epitaxy at 1010 oC, with B/(B+Al) gas-flow ratios ranging from 0.06 to 0.18. The boron content obtained from X-ray diffraction (XRD) patterns ranges from x = 0.02 to 0.09, while Rutherford backscattering spectrometry (RBS) measures x = 0.06 to 0.16. Transmission electron microscopy indicates the sole presence of the wurtzite crystal structure in the BAlN films, and a tendency towards twin formation and finer microstructure for B/(B+Al) gas-flow ratios greater than 0.15. The RBS data suggest that the incorporation of B is highly efficient, while the XRD data indicate that the epitaxial growth may be limited by a solubility limit in the crystal phase at about 9%. Electron energy loss spectroscopy has been used to profile spatial variations in the composition of the films. It has also located point defects in the films with nanometer resolution. The defects are identified as B and Al interstitials and N vacancies by comparison of the observed energy thresholds with results of density functional theory calculations.
The second part of this work investigates dislocation clusters observed in thick InxGa1-xN films with 0.07 ≤ x ≤ 0.12. The clusters resemble baskets with a higher indium content at their interior. Threading dislocations at the basket boundaries are of the misfit edge type, and their separation is consistent with misfit strain relaxation due the difference in indium content between the baskets and the surrounding matrix. The base of the baskets exhibits no observable misfit dislocations connected to the threading dislocations, and often no net displacements like those due to stacking faults. It is argued that the origin of these threading dislocation arrays is associated with misfit dislocations at the basal plane that dissociate, forming stacking faults. When the stacking faults form simultaneously satisfying the crystal symmetry, the sum of their translation vectors does add up to zero, consistent with our experimental observations.
The first part of this work is focused on the evolution of microstructures of BAlN thin films. The films were grown by flow-modulated epitaxy at 1010 oC, with B/(B+Al) gas-flow ratios ranging from 0.06 to 0.18. The boron content obtained from X-ray diffraction (XRD) patterns ranges from x = 0.02 to 0.09, while Rutherford backscattering spectrometry (RBS) measures x = 0.06 to 0.16. Transmission electron microscopy indicates the sole presence of the wurtzite crystal structure in the BAlN films, and a tendency towards twin formation and finer microstructure for B/(B+Al) gas-flow ratios greater than 0.15. The RBS data suggest that the incorporation of B is highly efficient, while the XRD data indicate that the epitaxial growth may be limited by a solubility limit in the crystal phase at about 9%. Electron energy loss spectroscopy has been used to profile spatial variations in the composition of the films. It has also located point defects in the films with nanometer resolution. The defects are identified as B and Al interstitials and N vacancies by comparison of the observed energy thresholds with results of density functional theory calculations.
The second part of this work investigates dislocation clusters observed in thick InxGa1-xN films with 0.07 ≤ x ≤ 0.12. The clusters resemble baskets with a higher indium content at their interior. Threading dislocations at the basket boundaries are of the misfit edge type, and their separation is consistent with misfit strain relaxation due the difference in indium content between the baskets and the surrounding matrix. The base of the baskets exhibits no observable misfit dislocations connected to the threading dislocations, and often no net displacements like those due to stacking faults. It is argued that the origin of these threading dislocation arrays is associated with misfit dislocations at the basal plane that dissociate, forming stacking faults. When the stacking faults form simultaneously satisfying the crystal symmetry, the sum of their translation vectors does add up to zero, consistent with our experimental observations.
ContributorsWang, Shuo, Ph.D (Author) / Ponce, Fernando A. (Thesis advisor) / Menéndez, Jose (Committee member) / Rez, Peter (Committee member) / McCartney, Martha (Committee member) / Arizona State University (Publisher)
Created2018
Description
Zeolites are a class of microporous materials that are immensely useful as molecular sieves and catalysts. While there exist millions of hypothetical zeolite topologies, only 206 have been recognized to exist in nature, and the question remains: What distinguishes known zeolite topologies from their hypothetical counterparts? It has been found that all 206 of the known zeolites can be represented as networks of rigid perfect tetrahedra that hinge freely at the connected corners. The range of configurations over which the corresponding geometric constraints can be met has been termed the "flexibility window". Only a small percentage of hypothetical types exhibit a flexibility window, and it is thus proposed that this simple geometric property, the existence of a flexibility window, provides a reliable benchmark for distinguishing potentially realizable hypothetical structures from their infeasible counterparts. As a first approximation of the behavior of real zeolite materials, the flexibility window provides additional useful insights into structure and composition. In this thesis, various methods for locating and exploring the flexibility window are discussed. Also examined is the assumption that the tetrahedral corners are force-free. This is a reasonable approximation in silicates for Si-O-Si angles above ~135°. However, the approximation is poor for germanates, where Ge-O-Ge angles are constrained to the range ~120°-145°. Lastly, a class of interesting low-density hypothetical zeolites is evaluated based on the feasibility criteria introduced.
ContributorsDawson, Colby (Author) / Treacy, Michael M. J. (Thesis advisor) / O'Keeffe, Michael (Committee member) / Thorpe, Michael F. (Committee member) / Rez, Peter (Committee member) / Bennett, Peter (Committee member) / Arizona State University (Publisher)
Created2013
Description
Nuclear proliferation concerns have resulted in a desire for radiation detectors with superior energy resolution. In this dissertation a Monte Carlo code is developed for calculating energy resolution in gamma-ray detector materials. The effects of basic material properties such as the bandgap and plasmon resonance energy are studied using a model for inelastic electron scattering based on electron energy-loss spectra. From a simplified "toy model" for a generic material, energy resolution is found to oscillate as the plasmon resonance energy is increased, and energy resolution can also depend on the valence band width. By incorporating the model developed here as an extension of the radiation transport code Penelope, photon processes are also included. The enhanced version of Penelope is used to calculate the Fano factor and average electron-hole pair energy in semiconductors silicon, gallium arsenide, zinc telluride, and scintillators cerium fluoride and lutetium oxyorthosilicate (LSO). If the effects of the valence band density-of-states and phonon scattering are removed, the calculated energy-resolution for these materials is fairly close to that for a toy model with a uniform electron energy-loss probability density function. This implies that the details of the electron cascade may in some cases have only a marginal effect on energy resolution.
ContributorsNarayan, Raman (Author) / Rez, Peter (Thesis advisor) / Spence, John (Committee member) / Ponce, Fernando (Committee member) / Comfort, Joseph (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2011
Description
Proton radiotherapy has recently become a popular form of cancer treatment. For maximum effectiveness, accurate models are needed to calculate proton angular scattering and energy loss. Scattering events are statistically independent and may be calculated from the effective number of events per reciprocal multiple scattering angle or energy loss. It is shown that multiple scattering distributions from Molière’s scattering law can be convolved by depth for accurate numerical calculation of angular distributions in several example materials. This obviates the need for correction factors to the analytic solution and its approximations. It is also shown that numerically solving Molière’s scattering law in terms of the complete (non-small angle) differential cross section and large angle approximations extends the validity of Molière theory to large angles. To calculate probability energy loss distributions, Landau-Vavilov theory is adapted to Fourier transforms and extended to very thick targets through convolution over the probability energy loss distributions in each depth interval. When the depth is expressed in terms of the continuous slowing down approximation (CSDA) the resulting probability energy loss distributions rely on the mean excitation energy as the sole material dependent parameter. Through numerical calculation of the CSDA over the desired energy loss, this allows the energy loss cross section to vary across the distribution and accurately accounts for broadening and skewness for thick targets in a compact manner. An analytic, Fourier transform solution to Vavilov’s integral is shown. A single scattering nuclear model that calculates large angle dose distributions that have a similar functional form to FLUKA (FLUktuierende KAskade) Monte Carlo, is also introduced. For incorporation into Monte Carlo or a treatment planning system, lookup tables of the number of scattering events or cross sections for different clinical energies may be used to determine angular or energy loss distributions.
ContributorsBrosch, Ryan Michael (Author) / Rez, Peter (Thesis advisor) / Alarcon, Ricardo O (Thesis advisor) / Vachaspati, Tanmay (Committee member) / Treacy, Michael M.J. (Committee member) / Arizona State University (Publisher)
Created2022
Description
Recent improvements in energy resolution for electron energy-loss spectroscopy in the scanning transmission electron microscope (STEM-EELS) allow novel effects in the low-loss region of the electron energy-loss spectrum to be observed. This dissertation explores what new information can be obtained with the combination of meV EELS energy resolution and atomic spatial resolution in the STEM. To set up this up, I review nanoparticle shape effects in the electrostatic approximation and compare the “classical” and “quantum” approaches to EELS simulation. Past the electrostatic approximation, the imaging of waveguide-type modes is modeled in ribbons and cylinders (in “classical" and “quantum" approaches, respectively), showing how the spatial variations of such modes can now be imaged using EELS. Then, returning to the electrostatic approximation, I present microscopic applications of low-loss STEM-EELS. I develop a “classical” model coupling the surface plasmons of a sharp metallic nanoparticle to the dipolar vibrations of an adsorbate molecule, which allows expected molecular signal enhancements to be quantified and the resultant Fano-type asymmetric spectral line shapes to be explained, and I present “quantum” modelling for the charged nitrogen-vacancy (NV-) and neutral silicon-vacancy (SiV0) color centers in diamond, including cross-sections and spectral maps from density functional theory. These results are summarized before concluding.
Many of these results have been previously published in Physical Review B. The main results of Ch. 2 and Ch. 4 were packaged as “Enhanced vibrational electron energy-loss spectroscopy of adsorbate molecules” (99, 104110), and much of Ch. 5 appeared as “Prospects for detecting individual defect centers using spatially resolved electron energy loss spectroscopy” (100, 134103). The results from Ch. 3 are being prepared for a forthcoming article in the Journal of Chemical Physics.
Many of these results have been previously published in Physical Review B. The main results of Ch. 2 and Ch. 4 were packaged as “Enhanced vibrational electron energy-loss spectroscopy of adsorbate molecules” (99, 104110), and much of Ch. 5 appeared as “Prospects for detecting individual defect centers using spatially resolved electron energy loss spectroscopy” (100, 134103). The results from Ch. 3 are being prepared for a forthcoming article in the Journal of Chemical Physics.
ContributorsKordahl, David Daniel (Author) / Dwyer, Christian (Thesis advisor) / Rez, Peter (Committee member) / Spence, John C.H. (Committee member) / Sukharev, Maxim (Committee member) / Arizona State University (Publisher)
Created2020
Description
This research evaluates the capabilities of typical radiological measures and dual-energy systems to differentiate common kidney stones materials: uric acid, oxalates, phosphates, struvite, and cystine. Two different X-ray spectra (80 kV and 120 kV) were applied and the dual-energy ratio of individual kidney stones was used to figure out the discriminability of different materials. A CT cross-section with a prospective kidney stone was analyzed to see the capabilities of such a technique. Typical radiological measures suggested that phosphates and oxalate stones can be distinguished from uric acid stones while dual-energy seemed to prove similar effectiveness.
ContributorsDelafuente, Nicholas William (Author) / Rez, Peter (Thesis director) / Alarcon, Ricardo (Committee member) / Department of Physics (Contributor) / Economics Program in CLAS (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05