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Description
Soft materials are matters that can easily deform from their original shapes and structures under thermal or mechanical stresses, and they range across various groups of materials including liquids, foams, gels, colloids, polymers, and biological substances. Although soft materials already have numerous applications with each of their unique characteristics, integrating

Soft materials are matters that can easily deform from their original shapes and structures under thermal or mechanical stresses, and they range across various groups of materials including liquids, foams, gels, colloids, polymers, and biological substances. Although soft materials already have numerous applications with each of their unique characteristics, integrating materials to achieve complementary functionalities is still a growing need for designing advanced applications of complex requirements. This dissertation explores a unique approach of utilizing intermolecular interactions to accomplish not only the multifunctionality from combined materials but also their tailored properties designed for specific tasks. In this work, multifunctional soft materials are explored in two particular directions, ionic liquids (ILs)-based mixtures and interpenetrating polymer network (IPN).

First, ILs-based mixtures were studied to develop liquid electrolytes for molecular electronic transducers (MET) in planetary exploration. For space missions, it is challenging to operate any liquid electrolytes in an extremely low-temperature environment. By tuning intermolecular interactions, the results demonstrated a facile method that has successfully overcome the thermal and transport barriers of ILs-based mixtures at extremely low temperatures. Incorporation of both aqueous and organic solvents in ILs-based electrolyte systems with varying types of intermolecular interactions are investigated, respectively, to yield optimized material properties supporting not only MET sensors but also other electrochemical devices with iodide/triiodide redox couple targeting low temperatures.

Second, an environmentally responsive hydrogel was synthesized via interpenetrating two crosslinked polymer networks. The intermolecular interactions facilitated by such an IPN structure enables not only an upper critical solution temperature (UCST) transition but also a mechanical enhancement of the hydrogel. The incorporation of functional units validates a positive swelling response to visible light and also further improves the mechanical properties. This studied IPN system can serve as a promising route in developing “smart” hydrogels utilizing visible light as a simple, inexpensive, and remotely controllable stimulus.

Over two directions across from ILs to polymeric networks, this work demonstrates an effective strategy of utilizing intermolecular interactions to not only develop multifunctional soft materials for advanced applications but also discover new properties beyond their original boundaries.
ContributorsXu, Yifei (Author) / Dai, Lenore L. (Thesis advisor) / Forzani, Erica (Committee member) / Holloway, Julianne (Committee member) / Jiang, Hanqing (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Two-dimensional quantum materials have garnered increasing interest in a wide

variety of applications due to their promising optical and electronic properties. These

quantum materials are highly anticipated to make transformative quantum sensors and

biosensors. Biosensors are currently considered among one of the most promising

solutions to a wide variety of biomedical and environmental problems

Two-dimensional quantum materials have garnered increasing interest in a wide

variety of applications due to their promising optical and electronic properties. These

quantum materials are highly anticipated to make transformative quantum sensors and

biosensors. Biosensors are currently considered among one of the most promising

solutions to a wide variety of biomedical and environmental problems including highly

sensitive and selective detection of difficult pathogens, toxins, and biomolecules.

However, scientists face enormous challenges in achieving these goals with current

technologies. Quantum biosensors can have detection with extraordinary sensitivity and

selectivity through manipulation of their quantum states, offering extraordinary properties

that cannot be attained with traditional materials. These quantum materials are anticipated

to make significant impact in the detection, diagnosis, and treatment of many diseases.

Despite the exciting promise of these cutting-edge technologies, it is largely

unknown what the inherent toxicity and biocompatibility of two-dimensional (2D)

materials are. Studies are greatly needed to lay the foundation for understanding the

interactions between quantum materials and biosystems. This work introduces a new

method to continuously monitor the cell proliferation and toxicity behavior of 2D

materials. The cell viability and toxicity measurements coupled with Live/Dead

fluorescence imaging suggest the biocompatibility of crystalline MoS2 and MoSSe

monolayers and the significantly-reduced cellular growth of defected MoTe2 thin films

and exfoliated MoS2 nanosheets. Results show the exciting potential of incorporating

kinetic cell viability data of 2D materials with other assay tools to further fundamental

understanding of 2D material biocompatibility.
ContributorsTran, Michael, Ph.D (Author) / Tongay, Sefaattin (Thesis advisor) / Green, Matthew (Thesis advisor) / Muhich, Christopher (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Interconnection methods for IBC photovoltaic (PV) module integration have widely been explored yet a concrete and cost-effective solution has yet to be found. Traditional methods of tabbing and stringing which are still being used today impart increased stress on the cells, not to mention the high temperatures induced during the

Interconnection methods for IBC photovoltaic (PV) module integration have widely been explored yet a concrete and cost-effective solution has yet to be found. Traditional methods of tabbing and stringing which are still being used today impart increased stress on the cells, not to mention the high temperatures induced during the soldering process as well. In this work and effective and economical interconnection method is demonstrated, by laser welding an embossed aluminum (Al) electrode layer to screen-printed silver (Ag) on the solar cell. Contact resistivity below 1mΩ.cm2 is measured with the proposed design. Cross-sectional analysis of interfaces is conducted via Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDXS) methods. Typical laser weld phenomenon observed involves Al ejection at the entrance of the weld, followed by Al and Ag fusing together mid-way through the weld spot, as revealed by cross-sectional depth analysis. The effects of voltage and lamp intensity are also tested on the welding process. With the range of voltages tested, 240V seems to show the least process variability and the most uniform contact between Al and Ag layers, upon using an Ethylene-Vinyl Acetate (EVA) encapsulant. Two lamp intensities were also explored with a Polyolefin (POE) encapsulant with Al and Ag layers seen welded together as well. Smaller effect sizes at lamp 2 intensity showed better contact. A process variability analysis was conducted to understand the effects of the two different lamps on welds being formed. Lamp 2 showed a bi-modal size distribution with a higher peak intensity, with more pulses coupling into the sample, as compared to lamp 1.
ContributorsSukumar Mony, Sujyot (Author) / Holman, Zachary (Thesis advisor) / Alford, Terry (Committee member) / Yu, Zhengshan (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Transition metal di- and tri-halides (TMH) have recently gathered research attention owing to their intrinsic magnetism all the way down to their two-dimensional limit. 2D magnets, despite being a crucial component for realizing van der Waals heterostructures and devices with various functionalities, were not experimentally proven until very recently in

Transition metal di- and tri-halides (TMH) have recently gathered research attention owing to their intrinsic magnetism all the way down to their two-dimensional limit. 2D magnets, despite being a crucial component for realizing van der Waals heterostructures and devices with various functionalities, were not experimentally proven until very recently in 2017. The findings opened up enormous possibilities for studying new quantum states of matter that can enable potential to design spintronic, magnetic memory, data storage, sensing, and topological devices. However, practical applications in modern technologies demand materials with various physical and chemical properties such as electronic, optical, structural, catalytic, magnetic etc., which cannot be found within single material systems. Considering that compositional modifications in 2D systems lead to significant changes in properties due to the high anisotropy inherent to their crystallographic structure, this work focuses on alloying of TMH compounds to explore the potentials for tuning their properties. In this thesis, the ternary cation alloys of Co(1-x)Ni(x)Cl(2) and Mo(1-x)Cr(x)Cl(3) were synthesized via chemical vapor transport at a various stoichiometry. Their compositional, structural, and magnetic properties were studied using Energy Dispersive Spectroscopy, Raman Spectroscopy, X-Ray Diffraction, and Vibrating Sample Magnetometry. It was found that completely miscible ternary alloys of Co(1-x)Ni(x)Cl(2) show an increasing Néel temperature with nickel concentration. The Mo(1-x)Cr(x)Cl(3) alloy shows potential magnetic phase changes induced by the incorporation of molybdenum species within the host CrCl3 lattice. Magnetic measurements give insight into potential antiferromagnetic to ferromagnetic transition with molybdenum incorporation, accompanied by a shift in the magnetic easy-axis from parallel to perpendicular. Phase separation was found in the Fe(1-x)Cr(x)Cl(3) ternary alloy indicating that crystallographic structure compatibility plays an essential role in determining the miscibility of two parent compounds. Alloying across two similar (TMH) compounds appears to yield predictable results in properties as in the case of Co(1-x)Ni(x)Cl(2), while more exotic transitions, as in the case of Mo(1-x)Cr(x)Cl(3), can emerge by alloying dissimilar compounds. When dissimilarity reaches a certain limit, as with Fe(1-x)Cr(x)Cl(3), phase separation becomes more favorable. Future studies focusing on magnetic and structural phase transitions will reveal more insight into the effect of alloying in these TMH systems.
ContributorsKolari, Pranvera (Author) / Tongay, Sefaattin (Thesis advisor) / Jiao, Yang (Committee member) / Muhich, Christopher (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Losses in commercial microwave dielectrics arise from spin excitations in paramagnetic transition metal dopants, at least at reduced temperatures. The magnitude of the loss tangent can be altered by orders of magnitude through the application of an external magnetic field. The goal of this thesis is to produce “smart” dielectrics

Losses in commercial microwave dielectrics arise from spin excitations in paramagnetic transition metal dopants, at least at reduced temperatures. The magnitude of the loss tangent can be altered by orders of magnitude through the application of an external magnetic field. The goal of this thesis is to produce “smart” dielectrics that can be switched “on” or “off” at small magnetic fields while investigating the influence of transition metal dopants on the dielectric, magnetic, and structural properties.

A proof of principle demonstration of a resonator that can switch from a high-Q “on state” to a low-Q “off state” at reduced temperatures is demonstrated in (Al1-xFex)2O3 and La(Al1-xFex)O3. The Fe3+ ions are in a high spin state (S=5/2) and undergo electron paramagnetic resonance absorption transitions that increase the microwave loss of the system. Transitions occur between mJ states with a corresponding change in the angular momentum, J, by ±ħ (i.e., ΔmJ=±1) at small magnetic fields. The paramagnetic ions also have an influence on the dielectric and magnetic properties, which I explore in these systems along with another low loss complex perovskite material, Ca[(Al1-xFex)1/2Nb1/2]O3. I describe what constitutes an optimal microwave loss switchable material induced from EPR transitions and the mechanisms associated with the key properties.

As a first step to modeling the properties of high-performance microwave host lattices and ultimately their performance at microwave frequencies, a first-principles approach is used to determine the structural phase stability of various complex perovskites with a range of tolerance factors at 0 K and finite temperatures. By understanding the correct structural phases of these complex perovskites, the temperature coefficient of resonant frequency can be better predicted.

A strong understanding of these parameters is expected to open the possibility to produce new types of high-performance switchable filters, time domain MIMO’s, multiplexers, and demultiplexers.
ContributorsGonzales, Justin Michael (Author) / Newman, Nathan (Thesis advisor) / Muhich, Christopher (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Flexible conducting materials have been in the forefront of a rapidly transforming electronics industry, focusing on wearable devices for a variety of applications in recent times. Over the past few decades, bulky, rigid devices have been replaced with a surging demand for thin, flexible, light weight, ultra-portable yet high performance

Flexible conducting materials have been in the forefront of a rapidly transforming electronics industry, focusing on wearable devices for a variety of applications in recent times. Over the past few decades, bulky, rigid devices have been replaced with a surging demand for thin, flexible, light weight, ultra-portable yet high performance electronics. The interconnects available in the market today only satisfy a few of the desirable characteristics, making it necessary to compromise one feature over another. In this thesis, a method to prepare a thin, flexible, and stretchable inter-connect is presented with improved conductivity compared to previous achievements. It satisfies most mechanical and electrical conditions desired in the wearable electronics industry. The conducting composite, prepared with the widely available, low cost silicon-based organic polymer - polydimethylsiloxane (PDMS) and silver (Ag), is sandwiched between two cured PDMS layers. These protective layers improve the mechanical stability of the inter-connect. The structure can be stretched up to 120% of its original length which can further be enhanced to over 250% by cutting it into a serpentine shape without compromising its electrical stability. The inter-connect, around 500 µm thick, can be integrated into thin electronic packaging. The synthesis process of the composite material, along with its electrical and mechanical and properties are presented in detail. Testing methods and results for mechanical and electrical stability are also illustrated over extensive flexing and stretching cycles. The materials put into test, along with conductive silver (Ag) - polydimethylsiloxane (PDMS) composite in a sandwich structure, are copper foils, copper coated polyimide (PI) and aluminum (Al) coated polyethylene terephthalate (PET).
ContributorsNandy, Mayukh (Author) / Yu, Hongbin (Thesis advisor) / Chan, Candace (Committee member) / Jiang, Hanqing (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Within the past two decades, metasurfaces, with their unique ability to tailor the wavefront, have attracted scientific attention. Along with many other research areas, RADAR cross-section (RCS)-reduction techniques have also benefited from metasurface technology.

In this dissertation, a novel technique to synthesize the RCS-reduction metasurfaces is presented. This technique unifies the

Within the past two decades, metasurfaces, with their unique ability to tailor the wavefront, have attracted scientific attention. Along with many other research areas, RADAR cross-section (RCS)-reduction techniques have also benefited from metasurface technology.

In this dissertation, a novel technique to synthesize the RCS-reduction metasurfaces is presented. This technique unifies the two most widely studied and two well-established modern RCS-reduction methods: checkerboard RCS-reduction andgradient-index RCS-reduction. It also overcomes the limitations associated with these RCS-reduction methods. It synthesizes the RCS-reduction metasurfaces, which can be juxtaposed with almost any existing metasurface, to reduce its RCS. The proposed technique is fundamentally based on scattering cancellation. Finally, an example of the RCS-reduction metasurface has been synthesized and introduced to reduce the RCS of an existing high-gain metasurface ground plane.

After that, various ways of obtaining ultrabroadband RCS-reduction using the same technique are proposed, which overcome the fundamental limitation of the conventional checkerboard metasurfaces, where the reflection phase difference of (180+-37) degrees is required to achieve 10-dB RCS reduction. First, the guideline on how to select Artificial Magnetic Conductors (AMCs) is explained with an example of a blended checkerboard architecture where a 10-dB RCS reduction is observed over 83% of the bandwidth. Further, by modifying the architecture of the blended checkerboard metasurface, the 10-dB RCS reduction bandwidth increased to 91% fractional bandwidth. All the proposed architectures are validated using measured data for fabricated prototypes. Critical steps for designing the ultrabroadband RCS reduction checkerboard surface are summarized.

Finally, a broadband technique to reduce the RCS of complex targets is presented. By using the proposed technique, the problem of reducing the RCS contribution from such multiple-bounces simplifies to identifying and implementing a set of orthogonal functions. Robust guidelines for avoiding grating lobes are provided using array theory. The 90 degree dihedral corner is used to verify the proposed technique. Measurements are reported for a fabricated prototype, where a 70% RCS-reduction bandwidth is observed. To generalize the method, a 45 degree dihedral corner, with a quadruple-bounce mechanism, is considered. Generalized guidelines are summarized and applied to reduce the RCS of complex targets using the proposed method.
ContributorsModi, Anuj (Author) / Balanis, Constantine A. (Thesis advisor) / Palais, Joseph C. (Committee member) / Aberle, James T. (Committee member) / Trichopoulos, Georgios C. (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Global industrialization and urbanization have led to increased levels of air pollution. The costs to society have come in the form of environmental damage, healthcare expenses, lost productivity, and premature mortality. Measuring pollutants is an important task for identifying its sources, warning individuals about dangerous exposure levels, and providing epidemiologists

Global industrialization and urbanization have led to increased levels of air pollution. The costs to society have come in the form of environmental damage, healthcare expenses, lost productivity, and premature mortality. Measuring pollutants is an important task for identifying its sources, warning individuals about dangerous exposure levels, and providing epidemiologists with data to link pollutants with diseases. Current methods for monitoring air pollution are inadequate though. They rely on expensive, complex instrumentation at limited fixed monitoring sites that do not capture the true spatial and temporal variation. Furthermore, the fixed outdoor monitoring sites cannot warn individuals about indoor air quality or exposure to chemicals at worksites. Recent advances in manufacturing and computing technology have allowed new classes of low-cost miniature gas sensor to emerge as possible alternatives. For these to be successful however, there must be innovations in the sensors themselves that improve reliability, operation, and their stability and selectivity in real environments. Three novel gas sensor solutions are presented. The first is the development of a wearable personal exposure monitor using all commercially available components, including two metal oxide semiconductor gas sensors. The device monitors known asthma triggers: ozone, total volatile organic compounds, temperature, humidity, and activity level. Primary focus is placed on the ozone sensor, which requires special circuits, heating algorithm, and calibration to remove temperature and humidity interferences. Eight devices are tested in multiple field tests. The second is the creation of a new compact optoelectronic gas sensing platform using colorimetric microdroplets printed on the surface of a complementary-metal-oxide-semiconductor (CMOS) imager. The nonvolatile liquid microdroplets provide a homogeneous, uniform environment that is ideal for colorimetric reactions and lensless optical measurements. To demonstrate one type of possible indicating system gaseous ammonia is detected by complexation with Cu(II). The third project continues work on the CMOS imager optoelectronic platform and develops a more robust sensing system utilizing hydrophobic aerogel particles. Ammonia is detected colorimetrically by its reaction with a molecular dye, with additives and surface treatments enhancing uniformity of the printed films. Future work presented at the end describes a new biological particle sensing system using the CMOS imager.
ContributorsMallires, Kyle Reed (Author) / Tao, Nongjian (Thesis advisor) / Forzani, Erica (Thesis advisor) / Wiktor, Peter (Committee member) / Wang, Di (Committee member) / Alford, Terry (Committee member) / Xian, Xiaojun (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Traditionally nanoporous gold is created by selective dissolution of silver or copper from a binary silver-gold or copper-gold alloy. These alloys serve as prototypical model systems for a phenomenon referred to as stress-corrosion cracking. Stress-corrosion cracking is the brittle failure of a normally ductile material occurring in a

Traditionally nanoporous gold is created by selective dissolution of silver or copper from a binary silver-gold or copper-gold alloy. These alloys serve as prototypical model systems for a phenomenon referred to as stress-corrosion cracking. Stress-corrosion cracking is the brittle failure of a normally ductile material occurring in a corrosive environment under a tensile stress. Silver-gold can experience this type of brittle fracture for a range of compositions. The corrosion process in this alloy results in a bicontinuous nanoscale morphology composed of gold-rich ligaments and voids often referred to as nanoporous gold. Experiments have shown that monolithic nanoporous gold can sustain high speed cracks which can then be injected into parent-phase alloy. This work compares nanoporous gold created from ordered and disordered copper-gold using digital image analysis and electron backscatter diffraction. Nanoporous gold from both disordered copper-gold and silver-gold, and ordered copper-gold show that grain orientation and shape remain largely unchanged by the dealloying process. Comparing the morphology of the nanoporous gold from ordered and disordered copper-gold with digital image analysis, minimal differences are found between the two and it is concluded that they are not statistically significant. This reveals the robust nature of nanoporous gold morphology against small variations in surface diffusion and parent-phase crystal structure.
Then the corrosion penetration down the grain boundary is compared to the depth of crack injections in polycrystal silver-gold. Based on statistical comparison, the crack-injections penetrate into the parent-phase grain boundary beyond the corrosion-induced porosity. To compare crack injections to stress-corrosion cracking, single crystal silver-gold samples are employed. Due to the cleavage-like nature of the fracture surfaces, electron backscatter diffraction is possible and employed to compare the crystallography of stress-corrosion crack surfaces and crack-injection surfaces. From the crystallographic similarities of these fracture surfaces, it is concluded that stress-corrosion can occur via a series of crack-injection events. This relationship between crack injections and stress corrosion cracking is further examined using electrochemical data from polycrystal silver-gold samples during stress-corrosion cracking. The results support the idea that crack injection is a mechanism for stress-corrosion cracking.
ContributorsKarasz, Erin (Author) / Sieradzki, Karl (Thesis advisor) / Chawla, Nikhilesh (Committee member) / Peralta, Pedro (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2020
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Description

The rationale of this thesis is to provide a thorough understanding of spalling for semiconductor materials and develop a low temperature spalling technology that reduces the surface roughness of the spalled wafers for Photovoltaics applications.

ContributorsGuimera Coll, Pablo (Author) / Bertoni, Mariana I (Thesis advisor) / Meier, Rico (Committee member) / Holman, Zachary (Committee member) / Wang, Qing Hua (Committee member) / Arizona State University (Publisher)
Created2020