Matching Items (52)
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
Description
Proton and fluorine diffusivity and ionic conductivity of 2-fluoropyridinium triflate (2-FPTf) and proton and fluorine diffusivity, ionic conductivity, and viscosity of trifluoromethanesulfonic acid (TFMSA) monohydrate have been measured over a wide range of temperatures. Diffusivities were measured using the pulsed-gradient spin-echo (PGSE) technique on a 300 MHz NMR spectrometer. Conductivities were measured using electrochemical impedance spectroscopy (EIS) on standard equipment and viscosities were determined using a Cannon-Ubbelohde viscometer. For 2-FPTF, the diffusivity of mobile protons increased from 1.84+/-0.06 x 10(-11) m2/s at 55 degC to 1.64+/-0.05 x 10(-10) m2/s at 115 degC while the diffusivity of 2-fluoropyridine fluorines increased from 2.22+/-0.07 x 10(-11) m2/s at 70 degC to 9.40+/-0.28 x 10(-11) m2/s at 115 degC. For TFMSA monohydrate, the diffusivity of protons increased from 7.67+/-0.23 x 10(-11) m2/s at 40 degC to 3.92+/-0.12 x 10(-10) m2/s at 110 degC while the diffusivity of fluorines increased from 4.63+/-0.14 x 10(-11) m2/s at 40 degC to 2.79+/-0.08 x 10(-10) m2/s at 110 degC, protons diffusing approximately 1.5 times faster than fluorines over the entire temperature range. NMR spectra indicate that proton diffusion occurs via direct hopping from TFMSA molecule to molecule. The conductivity of 2-FPTf varied from 0.85+/-0.03 mS/cm to 35.9+/-1.08 mS/cm between 25 and 110 degC. The conductivity of TFMSA monohydrate varied from 6.60+/-0.2 mS/cm to 84.6+/-2.5 mS/cm between 23 and 139 degC and its viscosity varied from 27.5+/-1.4 mPa.s to 4.38+/-0.22 mPa.s between 49 and 121.5 degC, in good agreement with literature values. Temperature dependences of the measured properties showed Arrhenius behavior with activation energies for proton diffusion, fluorine diffusion and ionic conduction for 2-FPTf above the melting point of 16.9+/-0.8 kJ/mol, 48.0+/-2.4 kJ/mol and 27.8+/-1.4 kJ/mol respectively. Activation energies for proton diffusion, fluorine diffusion, ionic conduction and viscosity for TFMSA monohydrate were 23.4+/-1.2 kJ/mol, 26.0+/-1.3 kJ/mol, 22.1+/-1.1 kJ/mol, and 26.9+/-1.3 kJ/mol respectively. The degree of dissociation of the charged species, calculated using the Nernst-Einstein relation, varied from 13 to 24% for 2-FPTf and from 25 to 29% for TFMSA monohydrate over the temperature range.
ContributorsAbdullah, Mohammed Wahed (Author) / Marzke, Robert F (Thesis advisor) / Gervasio, Dominic (Committee member) / Chamberlin, Ralph (Committee member) / Alarcon, Ricardo (Committee member) / Arizona State University (Publisher)
Created2015
Description
Wurtzite (In, Ga, Al) N semiconductors, especially InGaN material systems, demonstrate immense promises for the high efficiency thin film photovoltaic (PV) applications for future generation. Their unique and intriguing merits include continuously tunable wide band gap from 0.70 eV to 3.4 eV, strong absorption coefficient on the order of ∼105 cm−1, superior radiation resistance under harsh environment, and high saturation velocities and high mobility. Calculation from the detailed balance model also revealed that in multi-junction (MJ) solar cell device, materials with band gaps higher than 2.4 eV are required to achieve PV efficiencies greater than 50%, which is practically and easily feasible for InGaN materials. Other state-of-art modeling on InGaN solar cells also demonstrate great potential for applications of III-nitride solar cells in four-junction solar cell devices as well as in the integration with a non-III-nitride junction in multi-junction devices.
This dissertation first theoretically analyzed loss mechanisms and studied the theoretical limit of PV performance of InGaN solar cells with a semi-analytical model. Then three device design strategies are proposed to study and improve PV performance: band polarization engineering, structural design and band engineering. Moreover, three physical mechanisms related to high temperature performance of InGaN solar cells have been thoroughly investigated: thermal reliability issue, enhanced external quantum efficiency (EQE) and conversion efficiency with rising temperatures and carrier dynamics and localization effects inside nonpolar m-plane InGaN quantum wells (QWs) at high temperatures. In the end several future work will also be proposed.
Although still in its infancy, past and projected future progress of device design will ultimately achieve this very goal that III-nitride based solar cells will be indispensable for today and future’s society, technologies and society.
This dissertation first theoretically analyzed loss mechanisms and studied the theoretical limit of PV performance of InGaN solar cells with a semi-analytical model. Then three device design strategies are proposed to study and improve PV performance: band polarization engineering, structural design and band engineering. Moreover, three physical mechanisms related to high temperature performance of InGaN solar cells have been thoroughly investigated: thermal reliability issue, enhanced external quantum efficiency (EQE) and conversion efficiency with rising temperatures and carrier dynamics and localization effects inside nonpolar m-plane InGaN quantum wells (QWs) at high temperatures. In the end several future work will also be proposed.
Although still in its infancy, past and projected future progress of device design will ultimately achieve this very goal that III-nitride based solar cells will be indispensable for today and future’s society, technologies and society.
ContributorsHuang, Xuanqi (Author) / Zhao, Yuji (Thesis advisor) / Goodnick, Stephen M. (Committee member) / King, Richard R. (Committee member) / Vasileska, Dragica (Committee member) / Arizona State University (Publisher)
Created2020
Description
Programmable Metallization Cell (PMC) devices are, in essence, redox-based
solid-state resistive switching devices that rely on ion transport through a solid electrolyte (SE) layer from anode to cathode. Analysis and modeling of the effect of different fabrication and processing parameter/conditions on PMC devices are crucial for future electronics. Furthermore, this work is even more significant for devices utilizing back-end- of-line (BEOL) compatible materials such as Cu, W, their oxides and SiOx as these devices offer cost effectiveness thanks to their inherent foundry-ready nature. In this dissertation, effect of annealing conditions and cathode material on the performance of Cu-SiOx vertical devices is investigated which shows that W-based devices have much lower forming voltage and initial resistance values. Also, higher annealing temperatures first lead to an increase in forming voltage from 400 °C to 500 °C, then a drastic decrease at 550 °C due to Cu island formation at the Cu/SiOx interface. Next, the characterization and modeling of the bilayer Cu2O/Cu-WO3 obtained by annealing the deposited Cu/WO3 stacks in air at BEOL-compatible temperatures is presented that display unique characteristics for lateral PMC devices. First, thin film oxidation kinetics of Cu is studied which show a parabolic relationship with annealing time and an activation energy of 0.70 eV. Grown Cu2O shows a cauliflower-like morphology where feature size on the surface increase with annealing time and temperature. Then, diffusion kinetics of Cu in WO3 is examined where the activation energy of diffusion of Cu into WO3 is calculated to be 0.74 eV. Cu was found to form clusters in the WO3 host which was revealed by imaging. Moreover, using the oxidation and diffusion analyses, a Matlab model is established for modeling the bilayer for process and annealing-condition optimization. The model is built to produce the resulting Cu2O thickness and Cu concentration in Cu-WO3. Additionally, material characterization, preliminary electrical results along with modeling of lateral PMC devices utilizing the bilayer is also demonstrated. By tuning the process parameters such as deposited Cu thickness and annealing conditions, a low-resistive Cu2O layer was achieved which dramatically enhanced the electrodeposition growth rate for lateral PMC devices.
solid-state resistive switching devices that rely on ion transport through a solid electrolyte (SE) layer from anode to cathode. Analysis and modeling of the effect of different fabrication and processing parameter/conditions on PMC devices are crucial for future electronics. Furthermore, this work is even more significant for devices utilizing back-end- of-line (BEOL) compatible materials such as Cu, W, their oxides and SiOx as these devices offer cost effectiveness thanks to their inherent foundry-ready nature. In this dissertation, effect of annealing conditions and cathode material on the performance of Cu-SiOx vertical devices is investigated which shows that W-based devices have much lower forming voltage and initial resistance values. Also, higher annealing temperatures first lead to an increase in forming voltage from 400 °C to 500 °C, then a drastic decrease at 550 °C due to Cu island formation at the Cu/SiOx interface. Next, the characterization and modeling of the bilayer Cu2O/Cu-WO3 obtained by annealing the deposited Cu/WO3 stacks in air at BEOL-compatible temperatures is presented that display unique characteristics for lateral PMC devices. First, thin film oxidation kinetics of Cu is studied which show a parabolic relationship with annealing time and an activation energy of 0.70 eV. Grown Cu2O shows a cauliflower-like morphology where feature size on the surface increase with annealing time and temperature. Then, diffusion kinetics of Cu in WO3 is examined where the activation energy of diffusion of Cu into WO3 is calculated to be 0.74 eV. Cu was found to form clusters in the WO3 host which was revealed by imaging. Moreover, using the oxidation and diffusion analyses, a Matlab model is established for modeling the bilayer for process and annealing-condition optimization. The model is built to produce the resulting Cu2O thickness and Cu concentration in Cu-WO3. Additionally, material characterization, preliminary electrical results along with modeling of lateral PMC devices utilizing the bilayer is also demonstrated. By tuning the process parameters such as deposited Cu thickness and annealing conditions, a low-resistive Cu2O layer was achieved which dramatically enhanced the electrodeposition growth rate for lateral PMC devices.
ContributorsBalaban, Mehmet Bugra (Author) / Kozicki, Michael N (Thesis advisor) / Barnaby, Hugh J (Committee member) / Goryll, Michael (Committee member, Committee member) / Arizona State University (Publisher)
Created2020
Description
The structural and electronic properties of compositionally complex semiconductors have long been of both theoretical interest and engineering importance. As a new class of materials with an intrinsic compositional complexity, medium entropy alloys (MEAs) are immensely studied mainly for their excellent mechanical properties. The electronic properties of MEAs, however, are less well investigated. In this thesis, various properties such as electronic, spin, and thermal properties of two three-dimensional (3D) and two two-dimensional (2D) compositionally complex semiconductors are demonstrated to have promising various applications in photovoltaic, thermoelectric, and spin quantum bits (qubits).3D semiconducting Si-Ge-Sn and C3BN alloys is firstly introduced. Density functional theory (DFT) calculations and Monte Carlo simulations show that the Si1/3Ge1/3Sn1/3 MEA exhibits a large local distortion effect yet no chemical short-range order. Single vacancies in this MEA can be stabilized by bond reformations while the alloy retains semiconducting. DFT and molecular dynamics calculations predict that increasing the compositional disorder in SiyGeySnx MEAs enhances their electrical conductivity while weakens the thermal conductivity at room temperature, making the SiyGeySnx MEAs promising functional materials for thermoelectric devices. Furthermore, the nitrogen-vacancy (NV) center analog in C3BN (NV-C3BN) is studied to explore its applications in quantum computers. This analog possesses similar properties to the NV center in diamond such as a highly localized spin density and strong hyperfine interactions, making C3BN suitable for hosting spin qubits. The analog also displays two zero-phonon-line energies corresponding to wavelengths close to the ideal telecommunication band width, useful for quantum communications.
2D semiconducting transition metal chalcogenides (TMCs) and PtPN are also investigated. The quaternary compositionally complex TMCs show tunable properties such as in-plane lattice constants, band gaps, and band alignment, using a high through-put workflow from DFT calculations in conjunction with the virtual crystal approximation. A novel 2D semiconductor PtPN of direct bandgap is also predicted, based on pentagonal tessellation.
The work in the thesis offers guidance to the experimental realization of these novel semiconductors, which serve as valuable prototypes of other compositionally complex systems from other elements.
2D semiconducting transition metal chalcogenides (TMCs) and PtPN are also investigated. The quaternary compositionally complex TMCs show tunable properties such as in-plane lattice constants, band gaps, and band alignment, using a high through-put workflow from DFT calculations in conjunction with the virtual crystal approximation. A novel 2D semiconductor PtPN of direct bandgap is also predicted, based on pentagonal tessellation.
The work in the thesis offers guidance to the experimental realization of these novel semiconductors, which serve as valuable prototypes of other compositionally complex systems from other elements.
ContributorsWang, Duo (Author) / Zhuang, Houlong (Thesis advisor) / Singh, Arunima (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2020
Description
Lateral programmable metallization cells (PMC) utilize the properties of electrodeposits grown over a solid electrolyte channel. Such devices have an active anode and an inert cathode separated by a long electrodeposit channel in a coplanar arrangement. The ability to transport large amount of metallic mass across the channel makes these devices attractive for various More-Than-Moore applications. Existing literature lacks a comprehensive study of electrodeposit growth kinetics in lateral PMCs. Moreover, the morphology of electrodeposit growth in larger, planar devices is also not understood. Despite the variety of applications, lateral PMCs are not embraced by the semiconductor industry due to incompatible materials and high operating voltages needed for such devices. In this work, a numerical model based on the basic processes in PMCs – cation drift and redox reactions – is proposed, and the effect of various materials parameters on the electrodeposit growth kinetics is reported. The morphology of the electrodeposit growth and kinetics of the electrodeposition process are also studied in devices based on Ag-Ge30Se70 materials system. It was observed that the electrodeposition process mainly consists of two regimes of growth – cation drift limited regime and mixed regime. The electrodeposition starts in cation drift limited regime at low electric fields and transitions into mixed regime as the field increases. The onset of mixed regime can be controlled by applied voltage which also affects the morphology of electrodeposit growth. The numerical model was then used to successfully predict the device kinetics and onset of mixed regime. The problem of materials incompatibility with semiconductor manufacturing was solved by proposing a novel device structure. A bilayer structure using semiconductor foundry friendly materials was suggested as a candidate for solid electrolyte. The bilayer structure consists of a low resistivity oxide shunt layer on top of a high resistivity ion carrying oxide layer. Devices using Cu2O as the low resistivity shunt on top of Cu doped WO3 oxide were fabricated. The bilayer devices provided orders of magnitude improvement in device performance in the context of operating voltage and switching time. Electrical and materials characterization revealed the structure of bilayers and the mechanism of electrodeposition in these devices.
ContributorsChamele, Ninad (Author) / Kozicki, Michael (Thesis advisor) / Barnaby, Hugh (Committee member) / Newman, Nathan (Committee member) / Gonzalez-Velo, Yago (Committee member) / Arizona State University (Publisher)
Created2020
Description
Vibrational spectroscopy is a ubiquitous characterization tool in elucidating atomic structure at the bulk and nanoscale. The ability to perform high spatial resolution vibrational spectroscopy in a scanning transmission electron microscope (STEM) with electron energy-loss spectroscopy (EELS) has the potential to affect a variety of materials science problems. Since 2014, instrumentation development has pushed for incremental improvements in energy resolution, with the current best being 4.2 meV. Although this is poor in comparison to what is common in photon or neutron vibrational spectroscopies, the spatial resolution offered by vibrational EELS is equal to or better than the best of these other techniques.
The major objective of this research program is to investigate the spatial resolution of the monochromated energy-loss signal in the transmission-beam mode and correlate it to the excitation mechanism of the associated vibrational mode. The spatial variation of dipole vibrational signals in SiO2 is investigated as the electron probe is scanned across an atomically abrupt SiO2/Si interface. The Si-O bond stretch signal has a spatial resolution of 2 – 20 nm, depending on whether the interface, bulk, or surface contribution is chosen. For typical TEM specimen thicknesses, coupled surface modes contribute strongly to the spectrum. These coupled surface modes are phonon polaritons, whose intensity and spectral positions are strongly specimen geometry dependent. In a SiO2 thin-film patterned with a 2x2 array, dielectric theory simulations predict the simultaneous excitation of parallel and uncoupled surface polaritons and a very weak excitation of the orthogonal polariton.
It is demonstrated that atomic resolution can be achieved with impact vibrational signals from optical and acoustic phonons in a covalently bonded material like Si. Sub-nanometer resolution mapping of the Si-O symmetric bond stretch impact signal can also be performed in an ionic material like SiO2. The visibility of impact energy-loss signals from excitation of Brillouin zone boundary vibrational modes in hexagonal BN is seen to be a strong function of probe convergence, but not as strong a function of spectrometer collection angles. Some preliminary measurements to detect adsorbates on catalyst nanoparticle surfaces with minimum radiation damage in the aloof-beam mode are also presented.
The major objective of this research program is to investigate the spatial resolution of the monochromated energy-loss signal in the transmission-beam mode and correlate it to the excitation mechanism of the associated vibrational mode. The spatial variation of dipole vibrational signals in SiO2 is investigated as the electron probe is scanned across an atomically abrupt SiO2/Si interface. The Si-O bond stretch signal has a spatial resolution of 2 – 20 nm, depending on whether the interface, bulk, or surface contribution is chosen. For typical TEM specimen thicknesses, coupled surface modes contribute strongly to the spectrum. These coupled surface modes are phonon polaritons, whose intensity and spectral positions are strongly specimen geometry dependent. In a SiO2 thin-film patterned with a 2x2 array, dielectric theory simulations predict the simultaneous excitation of parallel and uncoupled surface polaritons and a very weak excitation of the orthogonal polariton.
It is demonstrated that atomic resolution can be achieved with impact vibrational signals from optical and acoustic phonons in a covalently bonded material like Si. Sub-nanometer resolution mapping of the Si-O symmetric bond stretch impact signal can also be performed in an ionic material like SiO2. The visibility of impact energy-loss signals from excitation of Brillouin zone boundary vibrational modes in hexagonal BN is seen to be a strong function of probe convergence, but not as strong a function of spectrometer collection angles. Some preliminary measurements to detect adsorbates on catalyst nanoparticle surfaces with minimum radiation damage in the aloof-beam mode are also presented.
ContributorsVenkatraman, Kartik (Author) / Crozier, Peter (Thesis advisor) / Rez, Peter (Committee member) / Wang, Robert (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2020
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
Two dimensional (2D) Janus Transition Metal Dichalcogenides (TMDs) are a new class of atomically thin polar materials. In these materials, the top and the bottom atomic layer are made of different chalcogen atoms. To date, several theoretical studies have shown that a broken mirror symmetry induces a colossal electrical field in these materials, which leads to unusual quantum properties. Despite these new properties, the current knowledge in their synthesis is limited only through two independent studies; both works rely on high-temperature processing techniques and are specific to only one type of 2D Janus material - MoSSe. Therefore, there is an urgent need for the development of a new synthesis method to (1) Extend the library of Janus class materials. (2) Improve the quality of 2D crystals. (3) Enable the synthesis of Janus heterostructures. The central hypothesis in this work is that the processing temperature of 2D Janus synthesis can be significantly lowered down to room temperatures by using reactive hydrogen and sulfur radicals while stripping off selenium atoms from the 2D surface. To test this hypothesis, a series of controlled growth studies were performed, and several complementary characterization techniques were used to establish a process–structure-property relationship. The results show that the newly proposed approach, namely Selective Epitaxy and Atomic Replacement (SEAR), is effective in reducing the growth temperature down to ambient conditions. The proposed technique benefits in achieving highly crystalline 2D Janus layers with an excellent optical response. Further studies herein show that this technique can form highly sophisticated lateral and vertical heterostructures of 2D Janus layers. Overall results establish an entirely new growth technique for 2D Janus.layers, which pave ways for the realization of exciting quantum effects in these materials such as Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) state, Majorana fermions, and topological p-wave superconductors.
ContributorsSayyad, Mohammed Yasir (Author) / Tongay, Sefaattin (Thesis advisor) / Crozier, Peter (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2020
Description
Physical vapor deposition (PVD) of phase-separating multicomponent alloy films generates a rich variety of unique self-organized nanoscale morphologies. However, an understanding of how the different material and process parameters influence the formation of these nanostructures is limited. My dissertation aims to bridge this gap by developing phase-field models that can predict an entire spectrum of nanostructures as a function of processing conditions and composition in multicomponent alloys under a set of material-specific constraints. Firstly, I developed a numerical model to simulate nanoscale phase separation in codeposited immiscible binary alloy films. An investigation on the influence of deposition rates, phase-fraction, and temperature, on the evolution of self-assembled nanostructures yielded many characteristic patterns, including well-known morphologies such as the lateral and vertical concentration modulations, as well as some previously undocumented variants. I also simulated phase-separation in ternary alloyed PVD films, and studied the influence of deposition rate and composition on the evolution of self-assembled nanostructures, and recorded many novel nanoscale morphologies. I then sought to understand the role of material properties such as elastic misfit due to lattice mismatch between phases, grain boundaries formed in polycrystalline films, and the interplay of interphase and surface boundaries at the film surface. To this end, I developed phase-field models of binary PVD film deposition that incorporated these constraints and studied their role in altering the temporal and spatial characteristics of the evolving morphologies. I also investigated the formation of surface hillocks and the role of surface and interfacial energies in their evolution. By studying the change in total free energy across the different deposition models, I established that, in addition to influencing the temporal and spatial characteristics of nanoscale structures in the films, this quantity is also responsible for driving morphological transitions as the rate of deposition is increased. Insights gained from this computational study will demonstrate the viability of these models in predicting experimentally observed morphologies and form a basis for understanding the various factors involved in driving phase-separation and morphological transitions. In addition, morphology maps will serve as templates for developing new pathways for morphology control in the manufacturing of PVD alloy films.
ContributorsRaghavan, Rahul (Author) / Ankit, Kumar (Thesis advisor) / Rajagopalan, Jagannathan (Committee member) / Mushongera, Leslie T (Committee member) / Arizona State University (Publisher)
Created2021