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Description
The work contained in this dissertation is focused on the optical properties of direct band gap semiconductors which crystallize in a wurtzite structure: more specifically, the III-nitrides and ZnO. By using cathodoluminescence spectroscopy, many of their properties have been investigated, including band gaps, defect energy levels, carrier lifetimes, strain states,

The work contained in this dissertation is focused on the optical properties of direct band gap semiconductors which crystallize in a wurtzite structure: more specifically, the III-nitrides and ZnO. By using cathodoluminescence spectroscopy, many of their properties have been investigated, including band gaps, defect energy levels, carrier lifetimes, strain states, exciton binding energies, and effects of electron irradiation on luminescence. Part of this work is focused on p-type Mg-doped GaN and InGaN. These materials are extremely important for the fabrication of visible light emitting diodes and diode lasers and their complex nature is currently not entirely understood. The luminescence of Mg-doped GaN films has been correlated with electrical and structural measurements in order to understand the behavior of hydrogen in the material. Deeply-bound excitons emitting near 3.37 and 3.42 eV are observed in films with a significant hydrogen concentration during cathodoluminescence at liquid helium temperatures. These radiative transitions are unstable during electron irradiation. Our observations suggest a hydrogen-related nature, as opposed to a previous assignment of stacking fault luminescence. The intensity of the 3.37 eV transition can be correlated with the electrical activation of the Mg acceptors. Next, the acceptor energy level of Mg in InGaN is shown to decrease significantly with an increase in the indium composition. This also corresponds to a decrease in the resistivity of these films. In addition, the hole concentration in multiple quantum well light emitting diode structures is much more uniform in the active region when Mg-doped InGaN (instead of Mg-doped GaN) is used. These results will help improve the efficiency of light emitting diodes, especially in the green/yellow color range. Also, the improved hole transport may prove to be important for the development of photovoltaic devices. Cathodoluminescence studies have also been performed on nanoindented ZnO crystals. Bulk, single crystal ZnO was indented using a sub-micron spherical diamond tip on various surface orientations. The resistance to deformation (the "hardness") of each surface orientation was measured, with the c-plane being the most resistive. This is due to the orientation of the easy glide planes, the c-planes, being positioned perpendicularly to the applied load. The a-plane oriented crystal is the least resistive to deformation. Cathodoluminescence imaging allows for the correlation of the luminescence with the regions located near the indentation. Sub-nanometer shifts in the band edge emission have been assigned to residual strain the crystals. The a- and m-plane oriented crystals show two-fold symmetry with regions of compressive and tensile strain located parallel and perpendicular to the ±c-directions, respectively. The c-plane oriented crystal shows six-fold symmetry with regions of tensile strain extending along the six equivalent a-directions.
ContributorsJuday, Reid (Author) / Ponce, Fernando A. (Thesis advisor) / Drucker, Jeff (Committee member) / Mccartney, Martha R (Committee member) / Menéndez, Jose (Committee member) / Shumway, John (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Microwave dielectrics are widely used to make resonators and filters in telecommunication systems. The production of thin films with high dielectric constant and low loss could potentially enable a marked reduction in the size of devices and systems. However, studies of these materials in thin film form are very sparse.

Microwave dielectrics are widely used to make resonators and filters in telecommunication systems. The production of thin films with high dielectric constant and low loss could potentially enable a marked reduction in the size of devices and systems. However, studies of these materials in thin film form are very sparse. In this research, experiments were carried out on practical high-performance dielectrics including ZrTiO4-ZnNb2O6 (ZTZN) and Ba(Co,Zn)1/3Nb2/3O3 (BCZN) with high dielectric constant and low loss tangent. Thin films were deposited by laser ablation on various substrates, with a systematical study of growth conditions like substrate temperature, oxygen pressure and annealing to optimize the film quality, and the compositional, microstructural, optical and electric properties were characterized. The deposited ZTZN films were randomly oriented polycrystalline on Si substrate and textured on MgO substrate with a tetragonal lattice change at elevated temperature. The BCZN films deposited on MgO substrate showed superior film quality relative to that on other substrates, which grow epitaxially with an orientation of (001) // MgO (001) and (100) // MgO (100) when substrate temperature was above 500 oC. In-situ annealing at growth temperature in 200 mTorr oxygen pressure was found to enhance the quality of the films, reducing the peak width of the X-ray Diffraction (XRD) rocking curve to 0.53o and the χmin of channeling Rutherford Backscattering Spectrometry (RBS) to 8.8% when grown at 800oC. Atomic Force Microscopy (AFM) was used to study the topography and found a monotonic decrease in the surface roughness when the growth temperature increased. Optical absorption and transmission measurements were used to determine the energy bandgap and the refractive index respectively. A low-frequency dielectric constant of 34 was measured using a planar interdigital measurement structure. The resistivity of the film is ~3×1010 ohm·cm at room temperature and has an activation energy of thermal activated current of 0.66 eV.
ContributorsLi, You (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Singh, Rakesh (Committee member) / Arizona State University (Publisher)
Created2013
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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 >

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.
ContributorsWertheim, Alex (Author) / Newman, Nathan (Thesis advisor) / Singh, Rakesh (Committee member) / Bertoni, Mariana (Committee member) / Arizona State University (Publisher)
Created2014
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Description
This thesis focuses on the theoretical work done to determine thermodynamic properties of a chalcopyrite thin-film material for use as a photovoltaic material in a tandem device. The material of main focus here is ZnGeAs2, which was chosen for the relative abundance of constituents, favorable photovoltaic properties, and good lattice

This thesis focuses on the theoretical work done to determine thermodynamic properties of a chalcopyrite thin-film material for use as a photovoltaic material in a tandem device. The material of main focus here is ZnGeAs2, which was chosen for the relative abundance of constituents, favorable photovoltaic properties, and good lattice matching with ZnSnP2, the other component in this tandem device. This work is divided into two main chapters, which will cover: calculations and method to determine the formation energy and abundance of native point defects, and a model to calculate the vapor pressure over a ternary material from first-principles. The purpose of this work is to guide experimental work being done in tandem to synthesize ZnGeAs2 in thin-film form with high enough quality such that it can be used as a photovoltaic. Since properties of photovoltaic depend greatly on defect concentrations and film quality, a theoretical understanding of how laboratory conditions affect these properties is very valuable. The work done here is from first-principles and utilizes density functional theory using the local density approximation. Results from the native point defect study show that the zinc vacancy (VZn) and the germanium antisite (GeZn) are the more prominent defects; which most likely produce non-stoichiometric films. The vapor pressure model for a ternary system is validated using known vapor pressure for monatomic and binary test systems. With a valid ternary system vapor pressure model, results show there is a kinetic barrier to decomposition for ZnGeAs2.
ContributorsTucker, Jon R (Author) / Van Schilfgaarde, Mark (Thesis advisor) / Newman, Nathan (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Doping and alloying agents are commonly used to engineer the properties of magnetic materials. This study investigates the effects of doping manganese in thin films of Ni80Fe20 (permalloy) and Ni65Fe15Co20 magnetic systems for low power memory technologies, including those that operate at low temperature.

Elemental manganese is anti-ferromagnetic with a

Doping and alloying agents are commonly used to engineer the properties of magnetic materials. This study investigates the effects of doping manganese in thin films of Ni80Fe20 (permalloy) and Ni65Fe15Co20 magnetic systems for low power memory technologies, including those that operate at low temperature.

Elemental manganese is anti-ferromagnetic with a Neel temperature of 100 K. When used as a dopant in a magnetic material, it is found to often align its moment in an antiferromagnetic direction. Thus, the addition of manganese might be expected to reduce the overall saturation magnetization (MS) of the magnetic system. In this study, we show that the use of manganese dopants in Ni80Fe20 (permalloy) and Ni65Fe15Co20 thin films can reduce their saturation magnetization and still retain excellent switching properties.

Magnetic properties and transport properties were determined using Vibrating Sample Magnetometer. A 19% decrease in the MS of (Ni80Fe20)1-xMnx thin films and a 36% decrease for (Ni65Fe15Co20)1-xMnx thin films for dopant levels of x = 30%. The impact of depositing a ruthenium (Ru) under-layer for (Ni65Fe15Co20)1-xMnx system was also studied.

The structural (lattice parameters and phases), surface (roughness and topography) and electrical properties (resistivity and mean free path) of the Mn-doped Ni65Fe15Co20 films were determined with X-Ray Diffraction, Atomic Force Microscopy and Four-Point probe technique respectively.

The properties were analyzed and Ni65Fe15Co20 system with Ru- under-layer with 20 at. % Mn content was found to exhibit the following low-field switching properties at 10 K; MS~700 emu.cm-3, easy axis coercivity ~10 Oe and hard axis coercivity ~5 Oe, easy axis squareness ~0.9 and anisotropy field ~12 Oe, that are deemed useful for low-power memory applications that could be used at cryogenic temperatures.

To determine the transport properties thought these magnetic layers for use in superconductor/ferromagnetic memory structures, a study of the oxidation conditions of Al films was performed in order to produce a reliable aluminum oxide tunnel barrier on top of these films. The production of N-I-F-S (Normal metal-Insulator-Ferromagnet-Superconductor) tunnel junctions will allow for the investigation of the tunneling density of states as a function of ferromagnetic layer thickness, allowing for the determination of important transport parameters relevant to magnetic barrier Josephson junction devices.
ContributorsBoochakravarthy, Ashwin Agathya (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry L. (Committee member) / Singh, Rakesh K. (Committee member) / Chamberlin, Ralph V (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Pyrite is a 0.95 eV bandgap semiconductor which is purported to have great potential in widespread, low–cost photovoltaic cells. A thorough material selection process was used in the design of a pyrite sequential vapor deposition chamber aimed at reducing and possibly eliminating contamination during thin film growth. The design process

Pyrite is a 0.95 eV bandgap semiconductor which is purported to have great potential in widespread, low–cost photovoltaic cells. A thorough material selection process was used in the design of a pyrite sequential vapor deposition chamber aimed at reducing and possibly eliminating contamination during thin film growth. The design process focused on identifying materials that do not produce volatile components when exposed to high temperatures and high sulfur pressures. Once the materials were identified and design was completed, the ultra–high vacuum growth system was constructed and tested.

Pyrite thin films were deposited using the upgraded sequential vapor deposition chamber by varying the substrate temperature from 250°C to 420°C during deposition, keeping sulfur pressure constant at 1 Torr. Secondary Ion Mass Spectrometry (SIMS) results showed that all contaminants in the films were reduced in concentration by orders of magnitude from those grown with the previous system. Characterization techniques of Rutherford Back–scattering Spectrometry (RBS), X–Ray Diffraction (XRD), Raman Spectroscopy, Optical Profilometry and UV/Vis/Near–IR Spectroscopy were performed on the deposited thin films. The results indicate that stoichiometric ratio of S:Fe, structural–quality (epitaxy), optical roughness and percentage of pyrite in the deposited thin films improve with increase in deposition temperature. A Tauc plot of the optical measurements indicates that the pyrite thin films have a bandgap of 0.94 eV.
ContributorsWalimbe, Aditya (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Singh, Rakesh (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The use of nanoparticle-in-matrix composites is a common motif among a broad range of nanoscience applications and is of particular interest to the thermal sciences community. To explore this morphological theme, crystalline inorganic composites were synthesized by mixing colloidal CdSe nanocrystals and In2Se3 metal chalcogenide complex (MCC) precursor in hydrazine

The use of nanoparticle-in-matrix composites is a common motif among a broad range of nanoscience applications and is of particular interest to the thermal sciences community. To explore this morphological theme, crystalline inorganic composites were synthesized by mixing colloidal CdSe nanocrystals and In2Se3 metal chalcogenide complex (MCC) precursor in hydrazine solvent and then thermally transform the MCC precursor into a crystalline In2Se3 matrix. The volume fraction of CdSe nanocrystals was varied from 0 to ~100% .Rich structural and chemical interactions between the CdSe nanocrystals and the In2Se3 matrix were observed. The average thermal conductivities of the 100% In2Se3 and ~100% CdSe composites are 0.32 and 0.53 W/m-K, respectively, which are remarkably low for inorganic crystalline materials. With the exception of the ~100% CdSe samples, the thermal conductivities of these nanocomposites are insensitive to CdSe volume fraction.This insensitivity is attributed to competing effects rise from structural morphology changes during composite formation.

Next, thermoelectric properties of metal chalcogenide thin films deposited from precursors using thiol-amine solvent mixtures were first reported. Cu2-xSeyS1-y and Ag-doped Cu2-xSeyS1-y thin films were synthesized, and the interrelationship between structure, composition, and room temperature thermoelectric properties was studied. The precursor annealing temperature affects the metal:chalcogen ratio, and leads to charge carrier concentration changes that affect Seebeck coefficient and electrical conductivity. Incorporating Ag into the Cu2-xSeyS1-y film leads to appreciable improvements in thermoelectric performance. Overall, the room temperature thermoelectric properties of these solution-processed materials are comparable to measurements on Cu2-xSe alloys made via conventional thermoelectric material processing methods.

Finally, a new route to make soluble metal chalcogenide precursors by reacting organic dichalcogenides with metal in different solvents was reported. By this method, SnSe, PbSe, SnTe and PbSexTe1-x precursors were successfully synthesized, and phase-pure and impurity-free metal chalcogenides were recovered after precursor decomposition. Compared to the hydrazine and diamine-dithiol route, the new approach uses safe solvent, and avoids introducing unwanted sulfur into the precursor. SnSe and PbSexTe1-x thin films, both of which are interesting thermoelectric materials, were also successfully made by solution deposition. The thermoelectric property measurements on those thin films show a great potential for future improvements.
ContributorsMa, Yuanyu (Author) / Wang, Robert (Thesis advisor) / Newman, Nathan (Committee member) / Wang, Liping (Committee member) / Hildreth, Owen (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The coexistence of superconductivity and ferromagnetic orders has been the subject of study for many years. It well known that these materials possess two competing order parameters; however the two order parameters can coexist under special circumstances inducing interesting physical phenomena. In recent years the demand of ultra-low-power, high density

The coexistence of superconductivity and ferromagnetic orders has been the subject of study for many years. It well known that these materials possess two competing order parameters; however the two order parameters can coexist under special circumstances inducing interesting physical phenomena. In recent years the demand of ultra-low-power, high density cryogenic memories has brought considerable interest to integrate superconducting and magnetic thin films in one structure to produce novel memory elements. The operation of the device depends on the unusual electronic properties associated with the Superconductor (S) /Ferromagnetic (F) proximity effect.

Niobium (Nb) based Josephson junction devices were fabricated with barriers containing two ferromagnetic layers separated by a normal metal space layer. In device operation, electrons in the superconductor are injected into the ferromagnets, causing the superconductor wavefunction to shift its phase and decay in amplitude. Such devices have two different states that depend on the relative magnetization of their ferromagnetic barrier layers, parallel or antiparallel. In these different states, the junctions have different phase shifts and critical currents. Superconducting circuits containing these devices can be designed to operate as memory cells using either one of these outputs.

To quantify the shift in phase and amplitude decay of the wavefunction through a common ferromagnet, permalloy, a series of Nb/permalloy/Nb Josephson junctions with varying ferromagnetic layer thicknesses were fabricated. Data have shown that the optimal thickness of a fixed layer composed of permalloy is 2.4 nm, as it shifts the wavefunction phase to π/2, its “pivot point.” If set to precisely this value, the free layer in SFNF'S junctions will switch the junction into either the 0 or π state depending on its magnetic orientation. To minimize the free-layer switching energy dilute Cu-permalloy alloy [Cu0.7(Ni80Fe20)0.3] with a low magnetic saturation (Ms of ~80 emu/cm3) was used as the free layer. These devices exhibit switching energies at small magnetic fields, demonstrating their potential use for low power non-volatile memory for superconductor circuits.

Lastly, to study the proximity effect using other potentially-useful ferromagnetic layers, measurements were performed on Nb/F bilayers and Nb/F/AlOx/Al tunnel junctions with ferromagnets Ni8Fe19, Ni65Fe15Co20, and Pd1-xNix. The dependence of the critical temperature of the bilayers and density of states that propagated through the ferromagnetic layer were studied as a function of thickness. From this study, crucial magnetic and electrical parameters like magnetic coherence lengths (ξF), exchange energy (Eex), and the rate of shift in the wavefunction’s phase and amplitude as a function of thickness were determined.
ContributorsAbd El Qader, Makram (Author) / Newman, Nathan (Thesis advisor) / Rowell, John (Committee member) / Rizzo, Nick (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2016
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Description
I studied the properties of novel Co2FeAl0.5Si0.5 (CFAS), ZnGeAs2, and FeS2 (pyrite) thin films for microelectronic applications ranging from spintronic to photovoltaic. CFAS is a half metal with theoretical spin polarization of 100%. I investigated its potential as a spin injector, for spintronic applications, by studying the critical steps involved

I studied the properties of novel Co2FeAl0.5Si0.5 (CFAS), ZnGeAs2, and FeS2 (pyrite) thin films for microelectronic applications ranging from spintronic to photovoltaic. CFAS is a half metal with theoretical spin polarization of 100%. I investigated its potential as a spin injector, for spintronic applications, by studying the critical steps involved in the injection of spin polarized electron populations from tunnel junctions containing CFAS electrodes. Epitaxial CFAS thin films with L21 structure and saturation magnetizations of over 1200 emu/cm3 were produced by optimization of the sputtering growth conditions. Point contact Andreev reflection measurements show that the spin polarization at the CFAS electrode surface exceeds 70%. Analyses of the electrical properties of tunnel junctions with a superconducting Pb counter-electrode indicate that transport through native Al oxide barriers is mostly from direct tunneling, while that through the native CFAS oxide barriers is not. ZnGeAs2 is a semiconductor comprised of only inexpensive and earth-abundant elements. The electronic structure and defect properties are similar in many ways to GaAs. Thus, in theory, efficient solar cells could be made with ZnGeAs2 if similar quality material to that of GaAs could be produced. To understand the thermochemistry and determine the rate limiting steps of ZnGeAs2 thin-film synthesis, the (a) thermal decomposition rate and (b) elemental composition and deposition rate of films were measured. It is concluded that the ZnGeAs2 thin film synthesis is a metastable process with an activation energy of 1.08±0.05 eV for the kinetically-limited decomposition rate and an evaporation coefficient of ~10-3. The thermochemical analysis presented here can be used to predict optimal conditions of ZnGeAs2 physical vapor deposition and thermal processing. Pyrite (FeS2) is another semiconductor that has tremendous potential for use in photovoltaic applications if high quality materials could be made. Here, I present the layer-by-layer growth of single-phase pyrite thin-films on heated substrates using sequential evaporation of Fe under high-vacuum followed by sulfidation at S pressures between 1 mTorr and 1 Torr. High-resolution transmission electron microscopy reveals high-quality, defect-free pyrite grains were produces by this method. It is demonstrated that epitaxial pyrite layer was produced on natural pyrite substrates with this method.
ContributorsVahidi, Mahmoud (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Singh, Rakesh (Committee member) / Chen, Tingyong (Committee member) / Arizona State University (Publisher)
Created2013
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Description
The object of this body of work is to study the properties and suitability of zinc oxide thin films with a view to engineering them for optoelectronics applications, making them a cheap and effective alternative to indium tin oxide (ITO), the most used transparent conducting oxides in the industry. Initially,

The object of this body of work is to study the properties and suitability of zinc oxide thin films with a view to engineering them for optoelectronics applications, making them a cheap and effective alternative to indium tin oxide (ITO), the most used transparent conducting oxides in the industry. Initially, a study was undertaken to examine the behavior of silver contacts to ZnO and ITO during thermal processing, a step frequently used in materials processing in optoelectronics. The second study involved an attempt to improve the conductivity of ZnO films by inserting a thin copper layer between two ZnO layers. The Hall resistivity of the films was as low as 6.9×10-5 -cm with a carrier concentration of 1.2×1022 cm-3 at the optimum copper layer thickness. The physics of conduction in the films has been examined. In order to improve the average visible transmittance, we replaced the copper layer with gold. The films were then found to undergo a seven orders of magnitude drop in effective resistivity from 200 -cm to 5.2×10-5 -cm The films have an average transmittance between 75% and 85% depending upon the gold thickness, and a peak transmittance of up to 93%. The best Haacke figure of merit was 15.1×10-3 . Finally, to test the multilayer transparent electrodes on a device, ZnO/Au/ZnO (ZAZ) electrodes were evaluated as transparent electrodes for organic light-emitting devices (OLEDs). The electrodes exhibited substantially enhanced conductivity (about 8×10-5 -cm) over conventional indium tin oxide (ITO) electrodes (about 3.2×10-5 -cm). OLEDs fabricated with the ZAZ electrodes showed reduced leakage compared to control OLEDs on ITO and reduced ohmic losses at high current densities. At a luminance of 25000 cd/m2, the lum/W efficiency of the ZAZ electrode based device improved by 5% compared to the device on ITO. A normalized intensity graph of the colour output from the green OLEDs shows that ZAZ electrodes allow for a broader spectral output in the green wavelength region of peak photopic sensitivity compared to ITO. The results have implications for electrode choice in display technology.
ContributorsSivaramakrishnan, Karthik (Author) / Alford, Terry L. (Thesis advisor) / Schroder, Dieter K. (Committee member) / Newman, Nathan (Committee member) / Theodore, David N (Committee member) / Arizona State University (Publisher)
Created2010