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- All Subjects: Materials Science
- Creators: Alford, Terry
- Status: Published
Description
Electron Paramagnetic Resonance (EPR) has facilitated great scientific advancements in many fields, like material science, engineering, medicine, biology, and health. EPR provided the ability to investigate samples on molecular level to detect chemical composition and identify harmful substances like free radicals. This thesis aims to explore current health and diagnostics EPR research and investigate the free radical content in related paramagnetic centers. Examining paramagnetic diagnostic markers of Cancer, Sicklecell disease, oxidative stress, and food oxidation. After exploring current literature on EPR, an experiment is designed and conducted to test seven different coffee samples (Turkish coffee, Espresso Coffee, European Coffee, Ground Arabic Coffee, American Coffee, Roasted Arabic Coffee, and Green Arabic Coffee), using Bruker ELEXSYS E580 spectrometer at x-band and under both room temperature (298 K) and low temperature (106 -113 K). Several microwave powers (1, mW, 0.25 mW, 0.16 mW, 0.06 mW, 0.04 mW) and different modulation frequency (10 G, 5 G, 3 G) are used. The results revealed average g-value was 2.009, highest linewidth was 16.312. Espresso coffee had the highest concentration of radicals, and green Arabic coffee beans had the lowest. Obtained spectra showed signals of Reactive Oxygen Species (ROS) radicals; believed to be result of natural oxidation process, as well as trace amounts of Fe3+ and other transition metals impurities, likely to be naturally found in coffee or resulting from the process of coffee production.
ContributorsMaki, Husain (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Chamberlin, Ralph (Committee member) / Arizona State University (Publisher)
Created2022
Description
Complex perovskite materials, including Ba(Zn1/3Ta2/3)O3 (BZT), are commonly used to make resonators and filters in communication systems because of their low dielectric loss and high-quality factors (Q). Transition metal additives are introduced (i.e., Ni2+, Co2+, Mn2+) to act as sintering agents and tune their temperature coefficient to zero or near-zero. However, losses in these commercial dielectric materials at cryogenic temperatures increase markedly due to spin-excitation resulting from the presence of paramagnetic defects. Applying a large magnetic field (e.g., 5 Tesla) quenches these losses and has allowed the study of other loss mechanisms present at low temperatures. Work was performed on Fe3+ doped LaAlO3. At high magnetic fields, the residual losses versus temperature plots exhibit Debye peaks at ~40 K, ~75 K, and ~215 K temperature and can be tentatively associated with defect reactions O_i^x+V_O^x→O_i^'+V_O^•, Fe_Al^x+V_Al^"→Fe_Al^'+V_Al^' and Al_i^x+Al_i^(••)→〖2Al〗_i^•, respectively. Peaks in the loss tangent versus temperature graph of Zn-deficient BZT indicate a higher concentration of defects and appear to result from conduction losses.Guided by the knowledge gained from this study, a systematic study to develop high-performance microwave materials for ultra-high performance at cryogenic temperatures was performed. To this end, the production and characterization of perovskite materials that were either undoped or contained non-paramagnetic additives were carried out. Synthesis of BZT ceramic with over 98% theoretical density was obtained using B2O3 or BaZrO3 additives. At 4 K, the highest Q x f product of 283,000 GHz was recorded for 5% BaZrO3 doped BZT.
A portable, inexpensive open-air spectrometer was designed, built, and tested to make the electron paramagnetic resonance (EPR) technique more accessible for high-school and university lab instruction. In this design, the sample is placed near a dielectric resonator and does not need to be enclosed in a cavity, as is used in commercial EPR spectrometers. Permanent magnets used produce fields up to 1500 G, enabling EPR measurements up to 3 GHz.
ContributorsGajare, Siddhesh Girish (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Tongay, Sefaattin (Committee member) / Chamberlin, Ralph (Committee member) / Arizona State University (Publisher)
Created2022
Description
Many important technologies, including electronics, computing, communications, optoelectronics, and sensing, are built on semiconductors. The band gap is a crucial factor in determining the electrical and optical properties of semiconductors. Beyond graphene, newly found two-dimensional (2D) materials have semiconducting bandgaps that range from the ultraviolet in hexagonal boron nitride to the terahertz and mid-infrared in bilayer graphene and black phosphorus, visible in transition metal dichalcogenides (TMDs). These 2D materials were shown to have highly controllable bandgaps which can be controlled by alloying. Only a small number of TMDs and monochalcogenides have been alloyed, though, because alloying compromised the material's Van der Waals (Vdw) property and the stability of the host crystal lattice phase. Phase transition in 2D materials is an interesting phenomenon where work has been done only on few TMDs namely MoTe2, MoS2, TaS2 etc.In order to change the band gaps and move them towards the UV (ultraviolet) and IR (infrared) regions, this work has developed new 2D alloys in InSe by alloying them with S and Te at 10% increasing concentrations. As the concentration of the chalcogens (S and Te) increased past a certain point, a structural phase transition in the alloys was observed. However, pinpointing the exact concentration for phase change and inducing phase change using external stimuli will be a thing of the future. The resulting changes in the crystal structure and band gap were characterized using some basic characterization techniques like scanning electron microscopy (SEM), X-ray Diffraction (XRD), Raman and photoluminescence spectroscopy.
ContributorsYarra, Anvesh Sai (Author) / Tongay, Sefaattin (Thesis advisor) / Yang, Sui (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2022
Description
Over the past three decades, significant progress in the development of organic light-emitting diodes (OLEDs) has been achieved, enabling OLEDs to become a main component in state-of-the-art displays and next generation solid-state lighting. As this technology advances, it is highly desirable to further improve the device efficiency and operational stability to drive the success of OLEDs in future display and lighting applications. This dissertation aims at developing novel organic emitting materials covering visible and near-infrared (NIR) emissions for efficient and table OLEDs. Firstly, a series of tetradentate Pd(II) complexes, which have attractive phosphorescent aggregate emission performance especially at high brightness level in device settings, have been developed. The luminescent lifetime of Pd(II) complex aggregates was demonstrated to be shorter than 1 μs with a close-to-unity photoluminescence quantum yield. Moreover, a systematic study regarding structure-property relationship was conducted on four tetradentate Pd(II) complexes, i.e., Pd3O3, Pd3O8-P, Pd3O8-Py2, and Pd3O8-Py5, featuring aggregate emission. As a result, an extremely efficient and stable OLED device utilizing Pd3O8-Py5 was achieved. It demonstrated a peak external quantum efficiency (EQE) of 37.3% with a reduced efficiency roll-off retaining a high EQE of 32.5% at 10000 cd m-2, and an estimated LT95 lifetime (time to 95% of the initial luminance) of 48246 h at 1000 cd m-2. Secondly, there is an increasing demand for NIR OLEDs with emission spectra beyond 900 nm to expand their applications in biometric authentication, night vision display, and telecommunication, etc. A stable and efficient NIR Pt(II) porphyrin complex named PtTPTNP-F8 was developed, and exhibited an electroluminescent spectrum at 920 nm. By carefully choosing the host materials, an PtTPTNP-F8 based NIR OLED achieved a EQE of 1.9%. Furthermore, an PtTPTNP-F8 OLED fabricated in a stable device structure demonstrated extraordinary operational stability with LT99 of >1000 h at 20 mA cm-2. Lastly, a series of imidazole-based blue Pt(II) complexes were developed and studied. Results indicated that structural modification of ligand molecules effectively tuned the emission spectral wavelength and bandwidth. Two blue complexes, i.e., Pt2O2 P2M and Pt2O2-PPy5-M, emitting at 472 and 476 nm respectively, exhibited narrow-band emission spectra with a full width at half maximum of 16 nm.
ContributorsCao, Linyu (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2021
Description
Highly reflective back surfaces are critical for reaching the detailed balance efficiency limits of photovoltaics. In addition to being highly reflective, the back surface and contact of the cell must have low resistance. A traditional approach to balance reflectance and contact resistance has been to use point contact geometries, which are process intensive. This work considers using a transparent conductive oxide and metal mirror, which, due to being two planar layers, can be fabricated much more easily. To study the tradeoff between resistance and absorptance for this contact, the oxide doping concentration is varied. Test structures to measure the doping concentration, contact resistance, and parasitic absorptance were fabricated. Using measured parameters, the performance of high-quality GaAs photonic power converters is modeled. Measurements show that although the contact resistance is comparatively high, it can be controlled through doping in the oxide and semiconductor composition. Furthermore, modeling shows the contact resistance is not prohibitively high for one-sun or lower illumination level devices. The hemispheric reflectance of the experimental oxide/metal back contact is modeled to be 96.7%, which is quite high considering that it is a conductive back contact. Although the oxide/metal contact structure does not perform electrically or optically as well as more complex point contact structures, this work indicates the advantages of the planar transparent conductive oxide/metal contact structure near one-sun equivalent current densities for solar cells and photonic power converters, where it is desirable to avoid the device fabrication costs of back contact patterning.
ContributorsGregory, Christopher Thomas (Author) / King, Richard R (Thesis advisor) / Goryll, Michael (Committee member) / Rolston, Nicholas (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2024
Description
Perovskite solar cells are one of the rising stars in the solar cell industry. This thesis explores several approaches to enhance the properties of the perovskite layer and the solar cell devices in which they operate. They include studies of different antisolvent additives during spin coating of triple cation perovskites, the use of surfactants to improve the quality of perovskite film microstructures, the applicability of a new fabrication process, and the value of post-deposition thermal and chemical annealing processes.This thesis experimentally analyzes different antisolvents, viz., ethyl acetate, isopropyl alcohol, toluene, and chlorobenzene. It focuses on the antisolvent-assisted crystallization method to achieve homogenous nucleation of the perovskite film. Of all the antisolvents, ethyl acetate-treated films gave the best-performing device, achieving a power conversion efficiency of 15.5%.
This thesis also analyzes the effects of mixed antisolvents on the qualities of triple-cation perovskites. Different solution concentrations of chlorobenzene in ethyl acetate and isopropyl alcohol in ethyl acetate are optimized for optimal supersaturation to achieve enlarged perovskite grains. Evaluations are discussed in the context of solution polarity and boiling point of the antisolvents, where 25% chlorobenzene in ethyl acetate antisolvent mixture shows the best film properties.
Another study discusses a new fabrication process called electrical field-assisted direct ink deposition for large-scale printing of perovskite solar cells. This process involves the formation of nanodroplets under an electrical field deposited onto ITO/glass substrates. As a result, smooth Poly (3,4-ethylene dioxythiophene) polystyrene sulfonate layers are
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produced with an average effective electrical resistivity of 4.15104 0.26 -m compared to that of spin-coated films.
A successive chapter discusses the studies of the electrical field-assisted direct ink deposition of the photoactive CH3NH3PbI2 (MAPbI3) layer. Its focus is on the post-deposition chemical annealing of the MAPbI3 films in methylamine gas, termed as methylamine gas-assisted healing and growth of perovskite films. This treatment improved the smoothness, reduced porosity, increased density, and generated more uniform grain sizes. Moreover, it improved the inter-grain boundary contacts by eliminating secondary, fine-grained boundary structures. Mechanisms behind the initial liquefaction of the MAPbI3 film's subsequent re-solidification are discussed.
ContributorsGogoi, Banashree (Author) / Alford, Terry (Thesis advisor) / Petuskey, William (Thesis advisor) / Gould, Ian (Committee member) / Li, Jian (Committee member) / Arizona State University (Publisher)
Created2023
Description
Diamond transistors are promising as high-power and high-frequency devices having higher efficiencies than conventional transistors. Diamond possesses superior electronic properties, such as a high bandgap (5.47 eV), high breakdown voltage (>10 MV cm−1 ), high electron and hole mobilities [4500 and 3800 cm2 V−1 · s−1, respectively], high electron and hole saturation velocities (1.5 × 107 and 1.05 × 107 cm s−1, respectively), and high thermal conductivity [22 W cm−1 · K−1], compared to conventional semiconductors. Reportedly, the diamond field-effect transistors (FETs) have shown transition frequencies (fT) of 45 and 70 GHz, maximum oscillation frequency (fmax) of 120 GHz, and radiofrequency (RF) power densities of 2.1 and 3.8 W mm−1 at 1 GHz. A two-dimensional-hole-gas (2DHG) surface channel forms on H-diamond by transfer doping from adsorbates/dielectrics in contact with H-diamond surface. However, prior studies indicate that charge transfer at the dielectric/ H-diamond interface could result in relatively low mobility attributed to interface scattering from the transferred negative charge to acceptor region. H-terminated diamond exhibits a negative electron affinity (NEA) of -1.1 to -1.3 eV, which is crucial to enable charge transfer doping. To overcome these limitations modulation doping, that is, selective doping, that leads to spatial separation of the MoO3 acceptor layer from the hole channel on H-diamond has been proposed. Molybdenum oxide (MoO3) was used as dielectric as it has electron affinity of 5.9eV and could align its conduction band minimum (CBM) below the valence band maximum (VBM) of H-terminated diamond. The band alignment provides the driving potential for charge transfer. Hafnium oxide (HfO2) was used as interfacial layer since it is a high-k oxide insulator (∼25), having large Eg (5.6 eV), high critical breakdown field, and high thermal stability. This study presents photoemission measurements of the electronic band alignments of the MoO3/HfO2/H-diamond layer structure to gain insight into the driving potential for the negative charge transfer and the location of the negative charges near the interface, in the HfO2 layer or in the MoO3 layer. The diamond hole concentration, mobility, and sheet resistance were characterized for MoO3/HfO2/H-Diamond with HfO2 layers of 0, 2 and 4 nm thickness.
ContributorsDeshmukh, Aditya Vilasrao (Author) / Nemanich, Robert J. (Thesis advisor) / Alford, Terry (Committee member) / Yang, Sui (Committee member) / Arizona State University (Publisher)
Created2024
Description
Global photovoltaic (PV) module installation in 2018 is estimated to exceed 100 GW, and crystalline Si (c-Si) solar cell-based modules have a share more than 90% of the global PV market. To reduce the social cost of PV electricity, further developments in reliability of solar panels are expected. These will lead to realize longer module lifetime and reduced levelized cost of energy. As many as 86 failure modes are observed in PV modules [1] and series resistance increase is one of the major durability issues of all. Series resistance constitutes emitter sheet resistance, metal-semiconductor contact resistance, and resistance across the metal-solder ribbon. Solder bond degradation at the cell interconnect is one of the primary causes for increase in series resistance, which is also considered to be an invisible defect [1]. Combination of intermetallic compounds (IMC) formation during soldering and their growth due to solid state diffusion over its lifetime result in formation of weak interfaces between the solar cell and the interconnect. Thermal cycling under regular operating conditions induce thermo-mechanical fatigue over these weak interfaces resulting in contact reduction or loss. Contact reduction or loss leads to increase in series resistance which further manifests into power and fill factor loss. The degree of intermixing of metallic interfaces and contact loss depends on climatic conditions as temperature and humidity (moisture ingression into the PV module laminate) play a vital role in reaction kinetics of these layers. Modules from Arizona and Florida served as a good sample set to analyze the effects of hot and humid climatic conditions respectively. The results obtained in the current thesis quantifies the thickness of IMC formation from SEM-EDS profiles, where similar modules obtained from different climatic conditions were compared. The results indicate the thickness of the IMC and detachment degree to be growing with age and operating temperatures of the module. This can be seen in CuxSny IMC which is thicker in the case of Arizona module. The results obtained from FL
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aged modules also show that humidity accelerates the formation of IMC as they showed thicker AgxSny layer and weak interconnect-contact interfaces as compared to Arizona modules. It is also shown that climatic conditions have different effects on rate at which CuxSny and AgxSny intermetallic compounds are formed.
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aged modules also show that humidity accelerates the formation of IMC as they showed thicker AgxSny layer and weak interconnect-contact interfaces as compared to Arizona modules. It is also shown that climatic conditions have different effects on rate at which CuxSny and AgxSny intermetallic compounds are formed.
ContributorsBuddha, Viswa Sai Pavan (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Alford, Terry (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Arizona State University (Publisher)
Created2018
Description
Recent technology advancements in photovoltaics have enabled crystalline silicon (c-Si) solar cells to establish outstanding photoconversion efficiency records. Remarkable progresses in research and development have been made both on the silicon feedstock quality as well as the technology required for surface passivation, the two dominant sources of performance loss via recombination of photo-generated charge carriers within advanced solar cell architectures.
As these two aspects of the solar cell framework improve, the need for a thorough analysis of their respective contribution under varying operation conditions has emerged along with challenges related to the lack of sensitivity of available characterization techniques. The main objective of my thesis work has been to establish a deep understanding of both “intrinsic” and “extrinsic” recombination processes that govern performance in high-quality silicon absorbers. By studying each recombination mechanism as a function of illumination and temperature, I strive to identify the lifetime limiting defects and propose a path to engineer the ultimate silicon solar cell.
This dissertation presents a detailed description of the experimental procedure required to deconvolute surface recombination contributions from bulk recombination contributions when performing lifetime spectroscopy analysis. This work proves that temperature- and injection-dependent lifetime spectroscopy (TIDLS) sensitivity can be extended to impurities concentrations down to 109 cm-3, orders of magnitude below any other characterization technique available today. A new method for the analysis of TIDLS data denominated Defect Parameters Contour Mapping (DPCM) is presented with the aim of providing a visual and intuitive tool to identify the lifetime limiting impurities in silicon material. Surface recombination velocity results are modelled by applying appropriate approaches from literature to our experimentally evaluated data, demonstrating for the first time their capability to interpret temperature-dependent data. In this way, several new results are obtained which solve long disputed aspects of surface passivation mechanisms. Finally, we experimentally evaluate the temperature-dependence of Auger lifetime and its impact on a theoretical intrinsically limited solar cell. These results decisively point to the need for a new Auger lifetime parameterization accounting for its temperature-dependence, which would in turn help understand the ultimate theoretical efficiency limit for a solar cell under real operation conditions.
As these two aspects of the solar cell framework improve, the need for a thorough analysis of their respective contribution under varying operation conditions has emerged along with challenges related to the lack of sensitivity of available characterization techniques. The main objective of my thesis work has been to establish a deep understanding of both “intrinsic” and “extrinsic” recombination processes that govern performance in high-quality silicon absorbers. By studying each recombination mechanism as a function of illumination and temperature, I strive to identify the lifetime limiting defects and propose a path to engineer the ultimate silicon solar cell.
This dissertation presents a detailed description of the experimental procedure required to deconvolute surface recombination contributions from bulk recombination contributions when performing lifetime spectroscopy analysis. This work proves that temperature- and injection-dependent lifetime spectroscopy (TIDLS) sensitivity can be extended to impurities concentrations down to 109 cm-3, orders of magnitude below any other characterization technique available today. A new method for the analysis of TIDLS data denominated Defect Parameters Contour Mapping (DPCM) is presented with the aim of providing a visual and intuitive tool to identify the lifetime limiting impurities in silicon material. Surface recombination velocity results are modelled by applying appropriate approaches from literature to our experimentally evaluated data, demonstrating for the first time their capability to interpret temperature-dependent data. In this way, several new results are obtained which solve long disputed aspects of surface passivation mechanisms. Finally, we experimentally evaluate the temperature-dependence of Auger lifetime and its impact on a theoretical intrinsically limited solar cell. These results decisively point to the need for a new Auger lifetime parameterization accounting for its temperature-dependence, which would in turn help understand the ultimate theoretical efficiency limit for a solar cell under real operation conditions.
ContributorsBernardini, Simone (Author) / Bertoni, Mariana I (Thesis advisor) / Coletti, Gianluca (Committee member) / Bowden, Stuart (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2018
Description
In this project, current-voltage (I-V) and Deep Level Transient Spectroscopy (DLTS) measurements are used to (a) characterize the electrical properties of Nb/p-type Si Schottky barriers, (b) identify the concentration and physical character of the electrically active defects present in the depletion region, and (c) use thermal processing to reduce the concentration or eliminate the defects. Barrier height determinations using temperature-dependent I-V measurements indicate that the barrier height decreases from 0.50 eV to 0.48 eV for anneals above 200 C. The electrically-active defect concentration measured using DLTS (deep level transient spectroscopy) drops markedly after anneals at 250 C.
A significant increase in leakage currents is almost always observed in near-ideal devices upon annealing. In contrast, non-ideal devices dominated by leakage currents annealed at 150 C to 250 C exhibit a significant decrease in such currents.
A significant increase in leakage currents is almost always observed in near-ideal devices upon annealing. In contrast, non-ideal devices dominated by leakage currents annealed at 150 C to 250 C exhibit a significant decrease in such currents.
ContributorsKrishna Murthy, Madhu (Author) / Newman, Nathan (Thesis advisor) / Goryll, Michael (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2018