Touch (or tactile) sensors are gaining renewed interest as the level of sophistication in the application of minimally invasive surgery and humanoid robots increases. The spatial resolution of current large-area tactile sensors (greater than 1 cm2) lag human fingers by over an order of magnitude. Using metal and semiconducting nanoparticles, a ~100 nm thick, large area thin-film device working on the principles of electron tunneling is self-assembled, such that the change in current density through the film and the electroluminescence light intensity are linearly proportional to the local stress. By pressing a United States 1 cent coin (and also a copper grid) on the device a well resolved stress image by focusing the electroluminescence light directly on CCD is obtained. Both the lateral and height resolution of texture are comparable to human finger at similar stress levels of ~10 KPa. The fabrication of the film is based on self-assembly of polyelectrolytes, and metal and semiconducting nanoparticles in a layered architecture. The polyelectrolyte layer functions as the dielectric tunneling barrier and the nanoparticles function as the base for tunneling electrons. The assembly of the device can be simplified by incorporating the functionality of the polyelectrolyte and the nanoparticles in a single composite medium. A non-micellar mineralization process for the synthesis of multifunctional nanocomposite materials is also reported as a possible building block for the assembly of tactile sensor. The non-micellar method results in the synthesis of monodisperse semi-conducting nanoparticles templated on polymer chains dissolved in solution at high yield. The monodispersity is achieved due to the beaded necklace morphology of the polyelectrolyte chains in solution where the beads are nanometer-scale nodules in the polymer chain and the nanoparticles are confined to the beads. The resultant structure is a nanoparticle studded necklace where the particles are imbedded in the beads. Multiple cycles of the synthesis on the polymer template yield nanoparticles of identical size, resulting in a nanocomposite with high particle fraction. The resultant nanocomposite has beaded-fibrilar morphology with imbedded nanoparticles, and can be solution cast to make electroluminescent thin film devices. The concept is further modified for synthesis of metal nanoparticles on polyelectrolyte templates with isolated beaded morphology. / Ph. D.

This dissertation describes new methods for measuring surface forces using evanescent waves, and applications to non-DLVO forces. An evanescent wave, generated at a solid-liquid interface, is scattered by AFM tips or particles attached to AFM cantilevers. The scattering of this wave is used to determine absolute separation between surfaces and/or the refractive index as a function of separation in AFM measurements. This technique is known as evanescent wave atomic force microscopy (EW-AFM). The scattering of an evanescent wave by Si3N4 AFM tips is large and decays exponentially with separation from a refractive index boundary. Thus, scattering is a useful method for measuring the separation between a Si3N4 tip and sample. This method has been used to measure the absolute separation between a tip and sample in the presence of an irreversibly adsorbed polymer film. Measurement of the film thickness and time response of the polymer to applied loads has also been studied. These measurements are not possible using current AFM techniques. In addition to measurements in polymer systems, the simple scattering profile from Si3N4 tips was used to re-examine short range hydration forces between hydrophilic surfaces. Results presented in this thesis suggest this force does not depend on the hydrated radius of the ion between glass and silicon nitride. The scattering generated by a Si3N4 tip has also been used to measure the refractive index of bulk fluids and thin films between hydrophobic surfaces. Based on these results, I have shown that a long-range attraction between hydrophobic surfaces is accompanied by an increase in the refractive index between the tip and surface. From this I have concluded that the attractive force, measured in this study, is the result of an increase in the concentration of organic material between surfaces. Finally, I have shown that the scattering profile depends on the material and size of the scattering object. Scattering from silicon nitride tips is exponential with separation. In contrast, the scattering profile from silicon tips, which are similar in size and geometry, is not a simple exponential. The scattering profile of larger spherical particles attached to cantilevers is also not exponential. It is approximately the sum of two exponentials. The functional form of the scattering profile with separation is consistent with the transmission of evanescent light through flat planar films. This result would suggest that a re-examination of the separation-dependence of scattering in TIRM measurements is necessary. / Ph. D.

Ionically self-assembled monolayer (ISAM) films are typically an assemblage of oppositely charged polymers built layer by layer through Coulombic attraction utilizing an environmentally friendly process to form ordered structures that are uniform, molecularly smooth and physically robust. ISAM films have been shown to be capable of the noncentrosymmetric order requisite for a second-order nonlinear optical response with excellent temporal and thermal stability. However, such films fabricated with a nonlinear optical (NLO) polyanion result in significant cancellation of the chromophore orientations. This cancellation occurs by two mechanisms: competitive orientation due to the ionic bonding of the polymer chromophore with the subsequent polycation layer, and random orientation of the chromophores within the bulk of each polyanion layer. A reduction in film thickness accompanied by an increase in net polar ordering is one possible avenue to obtain the second-order susceptibility chi(2) necessary for practical application in electro-optic devices. In this thesis, we discuss the structural characteristics of ISAM films and explore a novel approach to obtain the desired characteristics for nonlinear optical response. This approach involves a hybrid covalent / ionic self-assembly technique which affords improved net dipole alignment and concentration of monomer chromophores in the film. This technique yields a substantial increase in chi(2) due to the preferential chromophore orientation being locked in place by a covalent bond to the preceding polycation layer. The films fabricated in this manner yield a chi(2) that substantially exceeds that of any known polymer-polymer ISAM film. This covalent-hybrid ionically self-assembled multilayer (CHISAM) technique is demonstrated to result in films suitable for electro-optic devices, with measured electro-optic coefficient (14 pm/V) comparable to that of the inorganic crystal lithium niobate (30 pm/V). Thermal and temporal stability are important properties of electro-optic device implementation, and are demonstrated for CHISAM films. CHISAM films have remained stable at room temperature for more than 420 days, and suffered no loss of chi(2) when held at 80 C for 36 hours, followed by 150 C for 24 hours. Studies are also presented that demonstrate the ability to produce ISAM chi(2) films that are nearly one micron thick, and exhibit no evidence of a thickness limitation to the polar order. Analytical considerations for second-order NLO characterization of thick films are addressed in detail. The effect of absorption of the second harmonic wavelength and resonant enhancement of chi(2) are investigated, and it is demonstrated that accurate determination of chi(2) may be made for thick films and for films that absorb the second harmonic. The temporal and thermal stability of a variety of ISAM and CHISAM NLO films are examined in detail. In some cases, a decrease in the NLO response is observed at elevated temperature that is completely restored upon cooling. Studies are presented that suggest this effect is a result of thermally induced trans-to-cis isomerization of azo linkages in the NLO chromophores. / Ph. D.

Sapphire fiber has been studied intensively for harsh environment sensing in the past two decades due to its supreme mechanical, physical and optical properties. It is by far the most reported and likely the best optical fiber based sensing technology for sensing applications in temperature beyond 1000°C. Several sensing schemes have been proposed and studied to date including sapphire fiber extrinsic and intrinsic Fabry-Perot interferometers, fiber Bragg gratings and long period gratings inscribed in sapphire fibers. Lacking the cladding, sapphire fiber is highly multi-moded which renders sapphire fiber based sensor fabrication much more difficult than those based on silica fibers. Among all the reported work on sapphire fiber sensing, the vast majority is for single point temperature measurement. In this work, different sensing schemes are proposed to enhance the capability of the sapphire fiber based sensing technology. For the single point sensing, a miniaturized sapphire fiber temperature sensor for embedded sensing applications was proposed and studied. The sensors are no more than 75 µm in diameter and are ideal for non-invasive embedded sensing applications. Unlike existing sapphire fiber sensors, the thin film sensors are batch-fabrication oriented and thus have a potential to permit mass production with low cost. In addition to single point sensors, multiplexed sapphire fiber sensing systems are investigated for the first time. Two multiplexed sensing solutions, named frequency-multiplexing and spatial-multiplexing, are proposed and studied to achieve multiplexed sensing based on sapphire fibers. / Ph. D.

Developing high efficiency solar cells for lower manufacturing costs has been a key objective for photovoltaic researchers to drive down the levelized cost of energy for solar power. In this pursuit, III-V compound semiconductor based solar cells have steadily shown performance improvement at approximately 1% (absolute) increase per year, with a recent record efficiency of 46% under concentrator and 32% under AM0. However, the expensive cost has made it challenging for III-V solar cells to compete with the mainstream Silicon (Si) technology. Novel approaches to lower down the cost per watt for III-V solar cells will position them to be among the key contenders in the renewable energy sector. Integration of such high-efficiency III-V multijunction solar cells on significantly cheaper and large area Si substrate has the potential to address the future LCOE roadmaps by unifying the high-efficiency merits of III-V materials with low-cost and abundance of Si. However, the 4% lattice mismatch, thermal mismatch, polar on non-polar epitaxy makes the direct growth of GaAs on Si challenging, rendering the metamorphic cell sensitive to dislocations. The focus of this dissertation is to investigate heterogeneously integrated 1J GaAs solar cells on Si substrate using germanium (Ge) as an intermediate buffer layer that will address mitigation of defects and dislocations between GaAs active cell structure and Ge “virtual” substrate on Si. The all-epitaxial molecular beam epitaxy (MBE)-grown thin (<1 μm) hybrid GaAs/Ge “virtual” buffer approach provided 1J GaAs cell efficiency of ~10% on Si, as compared with cell structures with thick 3 μm GaAs buffers. Solar cell results were further corroborated with material analysis to provide a clear path for the reduction of performance limiting dislocations. The thin “Ge-on-Si” virtual buffer was then investigated comprehensively to understand the impact of the heterostructure on device performance. The growth, structural, morphological, and electrical transport properties of epitaxial thin-film Ge, grown by solid source MBE on Si using a two-step growth process, were investigated. High-resolution x-ray diffraction analysis demonstrated ~0.10% tensile strained Ge epilayer, owing to the thermal expansion coefficient mismatch between Ge and Si, and negligible epilayer lattice tilt due to misfit dislocations at the Ge/Si heterointerface. Micro-Raman spectroscopic analysis further corroborated the strain-state of the Ge thin-film on Si. Cross-sectional transmission electron microscopy revealed the formation of a 90° Lomer dislocation network at the Ge/Si heterointerface, suggesting the rapid and complete relaxation of the Ge epilayer during growth. Atomic force micrographs exhibited smooth surface morphologies with surface roughness < 2 nm. Hall mobility measurements, performed within a temperature range of 77 K to 315 K, and the modelling thereof indicated that ionized impurity scattering limited carrier mobility in the thin Ge epilayer. Additionally, capacitance- and conductance-voltage measurements were performed after fabricating the metal-oxide-semiconductor capacitors (MOS-Cs) in order to determine the effect of epilayer dislocation density on interfacial defect states (Dit), bulk trap density, and the energy distribution of Dit as a function of temperature for electronic device applications. Deep level transient spectroscopy was used to identify the location (within the Ge bandgap) of electrically active trap levels; however, no significant trap levels were detected. Finally, the extracted Dit values were benchmarked against previously reported Dit data for Ge MOS devices, as a function of threading dislocation density within the Ge layer. The results obtained in this work were found to be comparable with other Ge MOS devices integrated on Si via alternative buffer schemes. The understanding gained from this comprehensive study of Ge-on-Si will help optimize the 1J GaAs on Si via thin Ge buffer approach, to enable a future of high efficiency low cost solar cells for terrestrial applications. / Master of Science / The global energy landscape is projected to change remarkably in the coming decades with dwindling carbon based resource reserves and escalating energy demands, necessitating large-scale adoption of cleaner alternatives, such as solar energy. However, for widespread commercial and domestic adoption of photovoltaics, the cost of solar generated electricity must become competitive with non-renewable resources such as oil or coal. Thus, achieving high efficiency solar cells and driving down cell costs are key research objectives of the photovoltaic (PV) community in order to become more self-sufficient in the energy sector. In this pursuit, III-V compound semiconductor-based solar cells have steadily outperformed all other PV technologies, but cost-prohibitive for terrestrial deployment. Si is the undisputed standard in the PV industry; thus, to make a significant step forward in the pursuit of high efficiency solar cells, a promising approach will be to integrate the superior properties of compound semiconductors with the mature technology of Si. This research systematically investigates the integration of high efficiency III-V cells with low cost, abundant Si substrates via a germanium (Ge) layer to unify the performance merits of III-V cells with the cost benefits and superior mechanical and thermal properties of Si. Concurrently, Ge has also emerged as a strong candidate to boost transistor performance at low operating voltages, primarily owing to its superior carrier mobility and ease of integration into mainstream Si process flow. This research further delves into the structural and electrical properties of the Ge on Si structure. Overall, this research demonstrates the feasibility of the use of Ge directly integrated on Si for high efficiency solar cells and low-power electronic devices.

In the first part of this dissertation work, Al bond pad corrosion behavior was investigated in the presence of common industrial contaminants such as chloride (Cl-) and fluoride (F-). Al corrosion while in direct contact with Cu displayed rapid hydrogen (H2) gas evolution and dendrite propagation. In contrast, Al without bimetallic contact showed only minor surface roughening. This observed difference in the corrosion mechanism between Cl- and F- is attributed to the solubility of the corrosion products (AlCl3 vs. AlF3) formed on the Al surface. Our subsequent work explored corrosion prevention inhibition of wire-bonded devices (WBD) in the Cl- environment. Our research shows that the Al bond pad was protected against corrosion by chemically modifying the surface of the Cu wires, thereby preventing the H2 evolution. The inhibitor was observed to be highly selective, thermally stable, hydrophobic, and cost-effective, making it viable for industrial application of this coating for Al bond pad corrosion prevention. In the second part of the dissertation work, we utilized a novel approach of using ultraviolet-visible spectroscopy (UV-Vis) as a chemical-sensitive monitoring tool of the chemical environment in Cu etch bath. The UV-Vis technique illuminates the roles of H+, Cl-, Cu+, and Cu2+ to the etch bath while also providing a means to monitor the Cl- in the broad UV peak at 250 nm. The UV-Vis probe successfully demonstrated the etch rate difference between the two etch bath solutions and help in the restoration of the etching bath. Additionally, the proof-of-concept experiments (POC) to investigate UV enhanced etching for achieving anisotropic etching in PCB fabrication showed promising preliminary results with the need to develop additional etching techniques.

A fast response thin-film heat flux sensor was used to measure the time-resolved surface heat flux and temperature from a turbulent combustion flame impinging on a surface. Using the analytical semi-infinite conduction model, the unsteady surface heat flux was calculated from the transient temperature measurements and the surface temperature was calculated from the unsteady surface heat flux measurements. Methods of comparing time-resolved heat flux and temperature data were presented and discussed. The standard analytical method for converting surface temperature to heat flux was used. Two new analytical methods were developed for converting heat flux to surface temperature. The study is the first demonstration of time-resolved temperature signals generated from time-resolved heat flux measurements. The results graphically illustrate the effects of data processing on electrical noise present in the actual signal. The effect of flame unsteadiness is also shown, especially in the time-resolved heat flux measurements, which gives insight into the behavior of a propane torch. One application is for development of feed-forward control systems in industrial processes with fast transients. / Master of Science

The coupling of magnetic and electric order parameters, i.e., the magnetoelectric effect, has been widely studied for its intriguing physical principles and potentially broad industrial applications. The important interactions between ferroic orderings -- ferromagnetism, ferroelectricity and ferroelasticity -- will enable the manipulation of one order through the other in miniaturized materials, and in so doing stimulate emerging technologies such as spintronics, magnetic sensors, quantum electromagnets and information storage. By growing ferromagnetic-ferroelectric heterostructures that are able to magneto-electrically couple via interface elastic strain, the various challenges associated with the lack of single-phase multiferroic materials can be overcome and the magnetoelectric (ME) coupling effect can be substantially enhanced. Compared with magnetic field-controlled electric phenomena (i.e., the direct magnetoelectric coupling effect), the converse magnetoelectric effect (CME), whereby an electric field manipulates magnetization, is more exciting due to easier implementation and handling of electric fields or voltages. CME also affords the possibility of fabricating highly-efficient electric-write/magnetic-read memories. This study involved two avenues of inquiry: (a) exploring the strain-mediated electric field manipulation of magnetization in ferroelectric-ferromagnetic heterostructures, and (b) investigating coupling and switching behaviors at the nanoscale. Accordingly, a series of magnetoelectric heterostructures were prepared and characterized, and their electric field tunability of magnetic properties was explored by various techniques and custom-designed experiments. Firstly, the relevant properties of the individual components in the heterostructures were systematically investigated, including the piezoelectricity and ferroelectric/ferroelastic phase transformations of the ferroelectric substrates, lead magnesium niobate-lead titanate, or Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT). This investigation revealed significant information on the structure-property relationships in crystals oriented at <110>, as well as shed light on the effect of ferroelectric phase transformation on magnetoelectric coupling. This investigation of electric field controlled strain, in contrast to many prior studies, enables a more rational and detailed understanding of the magnetoelectric effect in complex ferroelectric-ferromagnetic heterostructures. The magnetoelectric thin film heterostructures were fabricated by depositing ferromagnetic iron-gallium (Fe-Ga) or cobalt ferrite (CoFe2o4 or CFO) films on top of differently-oriented ferroelectric PMN-PT substrates. Through significant electric field-induced strain in the piezoelectric substrate, the magnetic remanence and coercive field, as well as the magnetization direction of the ferromagnetic overlayer, can be substantially tuned. These goals were achieved by the interfacial strain modification of the magnetic anisotropy energy profile. The observation and analysis of the electric field tunability of magnetization and the establishment of novel controlling schemes provide valuable directions for both theoretical development and future application endeavors. / Master of Science

Ionically self-assembled monolayer (ISAM) films are typically an assemblage of oppositely charged polymers built layer by layer through coulombic attraction utilizing an environmentally friendly process to form ordered structures that are uniform, molecularly smooth, and physically robust. ISAM films have been shown to be capable of the noncentrosymmetric order requisite for a second-order nonlinear optical response. However, films fabricated with a nonlinear optical (NLO) polymer result in significant cancellation of the chromophore orientations. This cancellation occurs by two mechanisms: competitive orientation due to the ionic bonding of the polymer chromophore with the subsequent polycation layer, and random orientation of the chromophores within the bulk of each polyanion layer. A reduction in film thickness accompanied by an increase in net polar ordering is one possible avenue to obtain the second-order nonlinear optical susceptibility chi(2) necessary for electro-optic devices. In this thesis, we will discuss the structural characteristics of ISAM films and explore three novel approaches to obtain the desired characteristics for nonlinear optical response. One approach involves the variation of solution parameters of several different cationic polymers separately from the polyanion solution in order to reduce the competitive chromophore orientation at the layer interfaces and to reduce the thickness of the inactive polycation layer. We have found that the complexity of ISAM films does not allow large chi(2) values in polyion-based films, and that the selection of the polymer cation is vital to achieve second harmonic generation (SHG) at all. The second approach involves the incorporation of dianionic molecules into ISAM films in order to eliminate both competitive chromophore orientation and random chromophore orientation inherent with polymer chromophores. We have also studied the effects of complexing dianionic chromophores with beta-cyclodextrin in order to increase solubility and improve chromophore orientation. This approach fails because the outermost monolayer of dianionic chromophore is only tethered to the preceding polycation layer by a single ionic bond for each molecule, so each chromophore can by dissociated during the following immersion into the cation solution. Finally, we have introduced a novel approach of hybrid covalent / ionic self-assembly which overcomes these disadvantages and yields a substantial increase in chi(2) due to the chromophore being locked in place to the preceding polycation layer by a covalent bond. The films fabricated in this manner yield a chi(2) that rival any polymer-polymer films despite the very low first-order molecular hyperpolarizability beta of the incorporated monomer. This suggests that incorporation of high beta molecules may result in significant improvement of chi(2), holding high promise for the hybrid covalent / ionic self-assembly technique. / Master of Science

Multiferroics have attracted lots of research interest due to their potential in numerous multifunctional applications. The multiferroic materials could simultaneously exhibit two or more ferroic order parameters, and the coupling effects between ferroelectricity and ferromagnetism are named as magnetoelectric (ME) effect. Recently, with the development of thin film growth techniques, the multiferroics magnetoelectric composite heterostructures exhibit a very promising future prospects. This dissertation focused on the design, fabrication and characterization of new multiferroics magnetoelectric composite heterostructures. First, based on the specific phase architectures in BFO-CFO self-assembled thin films grown on variously oriented STO substrates and the epitaxial film growth knowledge, I designed two kinds of new film heterostructures: (i) I utilized self-assembled BFO nanopillars in a BFO-CFO two phase layer on (111) STO as a seed layer on which to deposit a secondary top BiFeO3 layer. The growth mechanism and multiferroic properties of these new heterostructures were investigated. (ii) I demonstrated the formation of a new quasi-(0-3) heterostructure by alternately growing (2-2) and (1-3) layers within the film. I proposed a new concept to overcome limitations of both the (2-2) and (1-3) phase connectivities and identified an indirect ME effect by the switching the characteristics of the piezoresponse for the new heterostructure. Second, for the option for candidates thin film materials with a high piezoelectric coefficient, which is a critical factor for ME composite films, I utilized the simple compositional BaSn0.11Ti0.89O3 bulk ceramic material as a target to grow films with the large piezoelectric properties. The grown high qualify lead-free epitaxial thin films had a chemical constituent similar to the reported giant piezoelectric ceramics near the MPB and with the QP. Both coherent and incoherent regions were observed in the interface and a larger piezoelectric coefficient d33 was achieved in this film. Finally, with respect to their characteristics and potential, I redirected from two-dimensional thin film materials to one-dimensional nanowire materials. By utilizing vertically aligned templates, I fabricated a new type of coaxial two-phase composite nanowires. Multiferroic properties of these new one-dimensional materials have been investigated. All these multiferroics magnetoelectric composite herterostructures would provide lots of potential in applications. / PHD