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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

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
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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

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
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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,

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 ii produced with an average effective electrical resistivity of 4.15104  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
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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

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
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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

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.
ContributorsBuddha, Viswa Sai Pavan (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Alford, Terry (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Arizona State University (Publisher)
Created2018
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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

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.
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
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Description
Being a remarkably versatile and inexpensive building material, concrete has found tremendous use in development of modern infrastructure and is the most widely used material in the world. Extensive research in the field of concrete has led to the development of a wide array of concretes with applications ranging from

Being a remarkably versatile and inexpensive building material, concrete has found tremendous use in development of modern infrastructure and is the most widely used material in the world. Extensive research in the field of concrete has led to the development of a wide array of concretes with applications ranging from building of skyscrapers to paving of highways. These varied applications require special cementitious composites which can satisfy the demand for enhanced functionalities such as high strength, high durability and improved thermal characteristics among others.

The current study focuses on the fundamental understanding of such functional composites, from their microstructural design to macro-scale application. More specifically, this study investigates three different categories of functional cementitious composites. First, it discusses the differences between cementitious systems containing interground and blended limestone with and without alumina. The interground systems are found to outperform the blended systems due to differential grinding of limestone. A novel approach to deduce the particle size distribution of limestone and cement in the interground systems is proposed. Secondly, the study delves into the realm of ultra-high performance concrete, a novel material which possesses extremely high compressive-, tensile- and flexural-strength and service life as compared to regular concrete. The study presents a novel first principles-based paradigm to design economical ultra-high performance concretes using locally available materials. In the final part, the study addresses the thermal benefits of a novel type of concrete containing phase change materials. A software package was designed to perform numerical simulations to analyze temperature profiles and thermal stresses in concrete structures containing PCMs.

The design of these materials is accompanied by material characterization of cementitious binders. This has been accomplished using techniques that involve measurement of heat evolution (isothermal calorimetry), determination and quantification of reaction products (thermo-gravimetric analysis, x-ray diffraction, micro-indentation, scanning electron microscopy, energy-dispersive x-ray spectroscopy) and evaluation of pore-size distribution (mercury intrusion porosimetry). In addition, macro-scale testing has been carried out to determine compression, flexure and durability response. Numerical simulations have been carried out to understand hydration of cementitious composites, determine optimum particle packing and determine the thermal performance of these composites.
ContributorsArora, Aashay (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Mobasher, Barzin (Committee member) / Chawla, Nikhilesh (Committee member) / Hoover, Christian G (Committee member) / Arizona State University (Publisher)
Created2018
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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

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.
ContributorsKrishna Murthy, Madhu (Author) / Newman, Nathan (Thesis advisor) / Goryll, Michael (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Chemical Vapor Deposition (CVD) is the most widely used method to grow large-scale single layer graphene. However, a systematic experimental study of the relationship between growth parameters and graphene film morphology, especially in the industrially preferred cold wall CVD, has not been undertaken previously. This research endeavored to address this

Chemical Vapor Deposition (CVD) is the most widely used method to grow large-scale single layer graphene. However, a systematic experimental study of the relationship between growth parameters and graphene film morphology, especially in the industrially preferred cold wall CVD, has not been undertaken previously. This research endeavored to address this and provide comprehensive insight into the growth physics of graphene on supported solid and liquid Cu films using cold wall CVD.

A multi-chamber UHV system was customized and transformed into a cold wall CVD system to perform experiments. The versatile growth process was completely custom-automated by controlling the process parameters with LabVIEW. Graphene growth was explored on solid electrodeposited, recrystallized and thin sputter deposited Cu films as well as on liquid Cu supported on W/Mo refractory substrates under ambient pressure using Ar, H₂ and CH₄ mixtures.

The results indicate that graphene grown on Cu films using cold wall CVD follows a classical two-dimensional nucleation and growth mechanism. The nucleation density decreases and average size of graphene crystallites increases with increasing dilution of the CH₄/H₂ mixture by Ar, decrease in total flow rate and decrease in CH₄:H₂ ratio at a fixed substrate temperature and chamber pressure. Thus, the resulting morphological changes correspond with those that would be expected if the precursor deposition rate was varied at a fixed substrate temperature for physical deposition using thermal evaporation. The evolution of graphene crystallite boundary morphology with decreasing effective C deposition rate indicates the effect of edge diffusion of C atoms along the crystallite boundaries, in addition to H₂ etching, on graphene crystallite shape.

The roles of temperature gradient, chamber pressure and rapid thermal heating in C precursor-rich environment on graphene growth morphology on thin sputtered Cu films were explained. The growth mechanisms of graphene on substrates annealed under reducing and non-reducing environment were explained from the scaling functions of graphene island size distribution in the pre-coalescence regime. It is anticipated that applying the pre-coalescence size distribution method presented in this work to other 2D material systems may be useful for elucidating atomistic mechanisms of film growth that are otherwise difficult to obtain.
ContributorsDas, Shantanu, Ph.D (Author) / Drucker, Jeff (Thesis advisor) / Alford, Terry (Committee member) / Chen, Tingyong (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Additive manufacturing (AM) describes an array of methods used to create a 3D object layer by layer. The increasing popularity of AM in the past decade has been due to its demonstrated potential to increase design flexibility, produce rapid prototypes, and decrease material waste. Temporary supports are an

Additive manufacturing (AM) describes an array of methods used to create a 3D object layer by layer. The increasing popularity of AM in the past decade has been due to its demonstrated potential to increase design flexibility, produce rapid prototypes, and decrease material waste. Temporary supports are an inconvenient necessity in many metal AM parts. These sacrificial structures are used to fabricate large overhangs, anchor the part to the build substrate, and provide a heat pathway to avoid warping. Polymers AM has addressed this issue by using support material that is soluble in an electrolyte that the base material is not. In contrast, metals AM has traditionally approached support removal using time consuming, costly methods such as electrical discharge machining or a dremel.

This work introduces dissolvable supports to single- and multi-material metals AM. The multi-material approach uses material choice to design a functionally graded material where corrosion is the functionality being varied. The single-material approach is the primary focus of this thesis, leveraging already common post-print heat treatments to locally alter the microstructure near the surface. By including a sensitizing agent in the ageing heat treatment, carbon is diffused into the part decreasing the corrosion resistance to a depth equal to at least half the support thickness. In a properly chosen electrolyte, this layer is easily chemically, or electrochemically removed. Stainless steel 316 (SS316) and Inconel 718 are both investigated to study this process using two popular alloys. The microstructure evolution and corrosion properties are investigated for both. For SS316, the effect of applied electrochemical potential is investigated to describe the varying corrosion phenomena induced, and the effect of potential choice on resultant roughness. In summary, a new approach to remove supports from metal AM parts is introduced to decrease costs and further the field of metals AM by expanding the design space.
ContributorsLefky, Christopher (Author) / Hildreth, Owen (Thesis advisor) / Chawla, Nikhilesh (Committee member) / Azeredo, Bruno (Committee member) / Rykaczewski, Konrad (Committee member) / Nian, Qiong (Committee member) / Arizona State University (Publisher)
Created2018