Study on fatigue and energy-dissipation properties of nanolayered Cu/Nb thin films

Energy dissipation and fatigue properties of nano-layered thin films are less well studied than bulk properties. Existing experimental methods for studying energy dissipation properties, typically using magnetic interaction as a driving force at different frequencies and a laser-based deformation measurement system, are difficult to apply to two-dimensional materials. We propose a novel experimental method to perform dynamic testing on thin-film materials by driving a cantilever specimen at its fixed end with a bimorph piezoelectric actuator and monitoring the displacements of the specimen and the actuator with a fibre-optic system. Upon vibration, the specimen is greatly affected by its inertia, and behaves as a cantilever beam under base excitation in translation. At resonance, this method resembles the vibrating reed method conventionally used in the viscoelasticity community. The loss tangent is obtained from both the width of a resonance peak and a free-decay process. As for fatigue measurement, we implement a control algorithm into LabView to maintain maximum displacement of the specimen during the course of the experiment. The fatigue S-N curves are obtained.

Modeling Optical Response of Thin Films: Choice of the Refractive Index Dispersion Law

Determination of the so-called optical constants (complex refractive index N, which is usually a function of the wavelength, and physical thickness D) of thin films from experimental data is a typical inverse non-linear problem. It is still a challenge to the scientific community because of the complexity of the problem and its basic and technological significance in optics. Usually, solutions are looked for models with 3-10 parameters. Best estimates of these parameters are obtained by minimization procedures. Herein, we discuss the choice of orthogonal polynomials for the dispersion law of the thin film refractive index. We show the advantage of their use, compared to the Selmeier, Lorentz or Cauchy models.

Insights into the influence of solvent polarity on the crystallization of poly(ethylene oxide) spin-coated thin films via in situ grazing incidence wide-angle X-ray scattering

Controlling polymer thin-film morphology and crystallinity is crucial for a wide range of applications, particularly in thin-film organic electronic devices. In this work, the crystallization behavior of a model polymer, poly(ethylene oxide) (PEO), during spin-coating is studied. PEO films were spun-cast from solvents possessing different polarities (chloroform, THF, and methanol) and probed via in situ grazing incidence wide-angle X-ray scattering. The crystallization behavior was found to follow the solvent polarity order (where chloroform < THF < methanol) rather than the solubility order (where THF > chloroform > methanol). When spun-cast from nonpolar chloroform, crystallization largely followed Avrami kinetics, resulting in the formation of morphologies comprising large spherulites. PEO solutions cast from more polar solvents (THF and methanol) do not form well-defined highly crystalline morphologies and are largely amorphous with the presence of small crystalline regions. The difference in morphological development of PEO spun-cast from polar solvents is attributed to clustering phenomena that inhibit polymer crystallization. This work highlights the importance of considering individual components of polymer solubility, rather than simple total solubility, when designing processing routes for the generation of morphologies with optimum crystallinities or morphologies.

Thin films fabricated from a nanoparticle beam

As time advances, man has been able to control technology in finer and finer detail. The microelectronics era is an example of this, with control down to the micrometer. Experts agree that we may be entering a new era, controlling technology down to the nanometer. One aspect of such control is making materials in the nanometer range, i.e. nanoparticles. For this purpose, a new magnetron-sputtering gun, inert gas condensation, nanoparticle source has been designed, built, and tested. ^ Films made from cobalt, nickel, tantalum, molybdenum, chromium, and aluminum have been investigated. Transmission Electron Microscope measurements done at the University of Illinois confirm the thin films are nanostructured. This was also confirmed by Atomic Force Microscope measurements made at the F.I.U. Thin Film Laboratory. ^ Composition, optical and magnetic properties have been measured. In most cases, unique properties have been found that differ significantly from bulk properties. Rutherford Backscattering measurements done at the University of Illinois determined significant percentages of oxygen and carbon in the samples, possibly due to interactions with air. Because of this, optical properties are a composite of oxide, metal, and void properties. Magnetic materials were determined to have spin-glass properties below the irreversibility temperature and superparamagnetic properties above it. Indications of possible future uses for these nanostructured materials are discussed. ^

Atomic vapor deposition of bismuth titanate thin films

c-axis oriented ferroelectric bismuth titanate (Bi4Ti 3O12) thin films were grown on (001) strontium titanate (SrTiO3) substrates by an atomic vapor deposition technique. The ferroelectric properties of the thin films are greatly affected by the presence of various kinds of defects. Detailed x-ray diffraction data and transmission electron microscopy analysis demonstrated the presence of out-of-phase boundaries (OPBs). It is found that the OPB density changes appreciably with the amount of titanium injected during growth of the thin films. Piezo-responses of the thin films were measured by piezo-force microscopy. It is found that the in-plane piezoresponse is stronger than the out-of-plane response, due to the strong c-axis orientation of the films.

The structural and piezoresponse properties of c-axis-oriented Aurivillius phase Bi5Ti3FeO15 thin films deposited by atomic vapor deposition

The deposition by atomic vapor deposition of highly c-axis-oriented Aurivillius phase Bi 5Ti 3FeO 15 (BTFO) thin films on (100) Si substrates is reported. Partially crystallized BTFO films with c-axis perpendicular to the substrate surface were first deposited at 610°C (8 excess Bi), and subsequently annealed at 820°C to get stoichiometric composition. After annealing, the films were highly c-axis-oriented, showing only (00l) peaks in x-ray diffraction (XRD), up to (0024). Transmission electron microscopy (TEM) confirms the BTFO film has a clear layered structure, and the bismuth oxide layer interleaves the four-block pseudoperovskite layer, indicating the n 4 Aurivillius phase structure. Piezoresponse force microscopy measurements indicate strong in-plane piezoelectric response, consistent with the c-axis layered structure, shown by XRD and TEM.

Optical properties of chiral thin films and microparticles

In this work I study the optical properties of helical particles and chiral sculptured thin films, using computational modeling (discrete dipole approximation, Berreman calculus), and experimental techniques (glancing angle deposition, ellipsometry, scatterometry, and non-linear optical measurements). The first part of this work focuses on linear optics, namely light scattering from helical microparticles. I study the influence of structural parameters and orientation on the optical properties of particles: circular dichroism (CD) and optical rotation (OR), and show that as a consequence of random orientation, CD and OR can have the opposite sign, compared to that of the oriented particle, potentially resulting in ambiguity of measurement interpretation. Additionally, particles in random orientation scatter light with circular and elliptical polarization states, which implies that in order to study multiple scattering from randomly oriented chiral particles, the polarization state of light cannot be disregarded. To perform experiments and attempt to produce particles, a newly constructed multi stage thin film coating chamber is calibrated. It enables the simultaneous fabrication of multiple sculptured thin film coatings, each with different structure. With it I successfully produce helical thin film coatings with Ti and TiO_{2}. The second part of this work focuses on non-linear optics, with special emphasis on second-harmonic generation. The scientific literature shows extensive experimental and theoretical work on second harmonic generation from chiral thin films. Such films are expected to always show this non-linear effect, due to their lack of inversion symmetry. However no experimental studies report non-linear response of chiral sculptured thin films. In this work I grow films suitable for a second harmonic generation experiment, and report the first measurements of non-linear response.

Dynamically mechanical and nano-impact (fatigue) analysis of touch screen thin films deposited on polyethylene terephthalate substrate

Nano-scale touch screen thin film have not been thoroughly investigated in terms of dynamic impact analysis under various strain rates. This research is focused on two different thin films, Zinc Oxide (ZnO) film and Indium Tin Oxide (ITO) film, deposited on Polyethylene Terephthalate (PET) substrate for the standard touch screen panels. Dynamic Mechanical Analysis (DMA) was performed on the ZnO film coated PET substrates. Nano-impact (fatigue) testing was performed on ITO film coated PET substrates. Other analysis includes hardness and the elastic modulus measurements, atomic force microscopy (AFM), Fourier Transform Infrared Spectroscopy (FTIR) and the Scanning Electron Microscopy (SEM) of the film surface.
Ten delta of DMA is described as the ratio of loss modulus (viscous properties) and storage modulus (elastic properties) of the material and its peak against time identifies the glass transition temperature (Tg). Thus, in essence the Tg recognizes changes from glassy to rubber state of the material and for our sample ZnO film, Tg was found as 388.3 K. The DMA results also showed that the Ten delta curve for Tg increases monotonically in the viscoelastic state (before Tg) and decreases sharply in the rubber state (after Tg) until recrystallization of ZnO takes place. This led to an interpretation that enhanced ductility can be achieved by negating the strength of the material.
For the nano-impact testing using the ITO coated PET, the damage started with the crack initiation and propagation. The interpretation of the nano-impact results depended on the characteristics of the loading history. Under the nano-impact loading, the surface structure of ITO film suffered from several forms of failure damages that range from deformation to catastrophic failures. It is concluded that in such type of application, the films should have low residual stress to prevent deformation, good adhesive strength, durable and good resistance to wear.

Multiferroic Iron Oxide Thin Films at Room Temperature

Multiferroic behaviour at room temperature is demonstrated in ε-Fe2O3. The simple composition of this new ferromagnetic ferroelectric oxide and the discovery of a robust path for its thin film growth by using suitable seed layers may boost the exploitation of ε-Fe2O3 in novel devices.

Spray Pyrolysed Tin Chalcogenide Thin Films: Optimization of optoelectronic properties of SnS for possible photovoltaic application as an absorber layer

In the early 19th century, industrial revolution was fuelled mainly by the development of machine based manufacturing and the increased use of coal. Later on, the focal point shifted to oil, thanks to the mass-production technology, ease of transport/storage and also the (less) environmental issues in comparison with the coal!! By the dawn of 21st century, due to the depletion of oil reserves and pollution resulting from heavy usage of oil the demand for clean energy was on the rising edge. This ever growing demand has propelled research on photovoltaics which has emerged successful and is currently being looked up to as the only solace for meeting our present day energy requirements. The proven PV technology on commercial scale is based on silicon but the recent boom in the demand for photovoltaic modules has in turn created a shortage in supply of silicon. Also the technology is still not accessible to common man. This has onset the research and development work on moderately efficient, eco-friendly and low cost photovoltaic devices (solar cells). Thin film photovoltaic modules have made a breakthrough entry in the PV market on these grounds. Thin films have the potential to revolutionize the present cost structure of solar cells by eliminating the use of the expensive silicon wafers that alone accounts for above 50% of total module manufacturing cost.

PEDOT:PSS thin films: Applications in Bioelectronics

Owing to their capability of merging the properties of metals and conventional polymers, Conducting Polymers (CPs) are a unique class of carbon-based materials capable of conducting electrical current. A conjugated backbone is the hallmark of CPs, which can readily undergo reversible doping to different extents, thus achieving a wide range of electrical conductivities, while maintaining mechanical flexibility, transparency and high thermal stability. Thanks to these inherent versatility and attracting properties, from their discovery CPs have experienced incessant widespread in a great plethora of research fields, ranging from energy storage to healthcare, also encouraging the spring and growth of new scientific areas with highly innovative content. Nowadays, Bioelectronics stands out as one of the most promising research fields, dealing with the mutual interplay between biology and electronics. Among CPs, the polyelectrolyte complex poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS), especially in the form of thin films, has been emphasized as ideal platform for bioelectronic applications. Indeed, in the last two decades PEDOT:PSS has played a key role in the sensing of bioanalytes and living cells interfacing and monitoring. In the present work, development and characterization of two kinds of PEDOT:PSS-based devices for applications in Bioelectronics are discussed in detail. In particular, a low-cost amperometric sensor for the selective detection of Dopamine in a ternary mixture was optimized, taking advantage of the electrocatalytic and antifouling properties that render PEDOT:PSS thin films appealing tools for electrochemical sensing of bioanalytes. Moreover, the potentialities of this material to interact with live cells were explored through the fabrication of a microfluidic trapping device for electrical monitoring of 3D spheroids using an impedance-based approach.

Greffage d’un film mince de nano-TiO2 sur les fibres naturelles cellulosiques pour le renforcement de biocomposites polymériques

Abstract : Natural materials have received a full attention in many applications because they are degradable and derived directly from earth. In addition to these benefits, natural materials can be obtained from renewable resources such as plants (i.e. cellulosic fibers like flax, hemp, jute, and etc). Being cheap and light in weight, the cellulosic natural fiber is a good candidate for reinforcing bio-based polymer composites. However, the hydrophilic nature -resulted from the presence of hydroxyl groups in the structure of these fibers- restricts the application of these fibers in the polymeric matrices. This is because of weak interfacial adhesion, and difficulties in mixing due to poor wettability of the fibers within the matrices. Many attempts have been done to modify surface properties of natural fibers including physical, chemical, and physico-chemical treatments but on the one hand, these treatments are unable to cure the intrinsic defects of the surface of the fibers and on the other hand they cannot improve moisture, and alkali resistance of the fibers. However, the creation of a thin film on the fibers would achieve the mentioned objectives. This study aims firstly to functionalize the flax fibers by using selective oxidation of hydroxyl groups existed in cellulose structure to pave the way for better adhesion of subsequent amphiphilic TiO[subscript 2] thin films created by Sol-Gel technique. This method is capable of creating a very thin layer of metallic oxide on a substrate. In the next step, the effect of oxidation on the interfacial adhesion between the TiO[subscript 2] film and the fiber and thus on the physical and mechanical properties of the fiber was characterized. Eventually, the TiO[subscript 2] grafted fibers with and without oxidation were used to reinforce poly lactic acid (PLA). Tensile, impact, and short beam shear tests were performed to characterize the mechanical properties while Thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC), Dynamic mechanical analysis (DMA), and moisture absorption were used to show the physical properties of the composites. Results showed a significant increase in physical and mechanical properties of flax fibers when the fibers were oxidized prior to TiO[subscript 2] grafting. Moreover, the TiO[subscript 2] grafted oxidized fiber caused significant changes when they were used as reinforcements in PLA. A higher interfacial strength and less amount of water absorption were obtained in comparison with the reference samples.

Engineering thin films of magnetic alloys and semiconductor oxides at the nanoscale

The thesis aims to exploit properties of thin films for applications such as spintronics, UV detection and gas sensing. Nanoscale thin films devices have myriad advantages and compatibility with Si-based integrated circuits processes. Two distinct classes of material systems are investigated, namely ferromagnetic thin films and semiconductor oxides. To aid the designing of devices, the surface properties of the thin films were investigated by using electron and photon characterization techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), grazing incidence X-ray diffraction (GIXRD), and energy-dispersive X-ray spectroscopy (EDS). These are complemented by nanometer resolved local proximal probes such as atomic force microscopy (AFM), magnetic force microscopy (MFM), electric force microscopy (EFM), and scanning tunneling microscopy to elucidate the interplay between stoichiometry, morphology, chemical states, crystallization, magnetism, optical transparency, and electronic properties. Specifically, I studied the effect of annealing on the surface stoichiometry of the CoFeB/Cu system by in-situ AES and discovered that magnetic nanoparticles with controllable areal density can be produced. This is a good alternative for producing nanoparticles using a maskless process. Additionally, I studied the behavior of magnetic domain walls of the low coercivity alloy CoFeB patterned nanowires. MFM measurement with the in-plane magnetic field showed that, compared to their permalloy counterparts, CoFeB nanowires require a much smaller magnetization switching field , making them promising for low-power-consumption domain wall motion based devices. With oxides, I studied CuO nanoparticles on SnO2 based UV photodetectors (PDs), and discovered that they promote the responsivity by facilitating charge transfer with the formed nanoheterojunctions. I also demonstrated UV PDs with spectrally tunable photoresponse with the bandgap engineered ZnMgO. The bandgap of the alloyed ZnMgO thin films was tailored by varying the Mg contents and AES was demonstrated as a surface scientific approach to assess the alloying of ZnMgO. With gas sensors, I discovered the rf-sputtered anatase-TiO2 thin films for a selective and sensitive NO2 detection at room temperature, under UV illumination. The implementation of UV enhances the responsivity, response and recovery rate of the TiO2 sensor towards NO2 significantly. Evident from the high resolution XPS and AFM studies, the surface contamination and morphology of the thin films degrade the gas sensing response. I also demonstrated that surface additive metal nanoparticles on thin films can improve the response and the selectivity of oxide based sensors. I employed nanometer-scale scanning probe microscopy to study a novel gas senor scheme consisting of gallium nitride (GaN) nanowires with functionalizing oxides layer. The results suggested that AFM together with EFM is capable of discriminating low-conductive materials at the nanoscale, providing a nondestructive method to quantitatively relate sensing response to the surface morphology.

Computational modeling of laser-induced delamination testing of thin films

Thin film adhesion often determines microelectronic device reliability and it is therefore essential to have experimental techniques that accurately and efficiently characterize it. Laser-induced delamination is a novel technique that uses laser-generated stress waves to load thin films at high strain rates and extract the fracture toughness of the film/substrate interface. The effectiveness of the technique in measuring the interface properties of metallic films has been documented in previous studies. The objective of the current effort is to model the effect of residual stresses on the dynamic delamination of thin films. Residual stresses can be high enough to affect the crack advance and the mode mixity of the delimitation event, and must therefore be adequately modeled to make accurate and repeatable predictions of fracture toughness. The equivalent axial force and bending moment generated by the residual stresses are included in a dynamic, nonlinear finite element model of the delaminating film, and the impact of residual stresses on the final extent of the interfacial crack, the relative contribution of shear failure, and the deformed shape of the delaminated film is studied in detail. Another objective of the study is to develop techniques to address issues related to the testing of polymeric films. These type of films adhere well to silicon and the resulting crack advance is often much smaller than for metallic films, making the extraction of the interface fracture toughness more difficult. The use of an inertial layer which enhances the amount of kinetic energy trapped in the film and thus the crack advance is examined. It is determined that the inertial layer does improve the crack advance, although in a relatively limited fashion. The high interface toughness of polymer films often causes the film to fail cohesively when the crack front leaves the weakly bonded region and enters the strong interface. The use of a tapered pre-crack region that provides a more gradual transition to the strong interface is examined. The tapered triangular pre-crack geometry is found to be effective in reducing the stresses induced thereby making it an attractive option. We conclude by studying the impact of modifying the pre-crack geometry to enable the testing of multiple polymer films.

Thin films of Cu, In and Sb chalcogenides as photovoltaic absorbers

Many different photovoltaic technologies are being developed for large-scale solar energy conversion such as crystalline silicon solar cells, thin film solar cells based on a-Si:H, CIGS and CdTe. As the demand for photovoltaics rapidly increases, there is a pressing need for the identification of new visible light absorbing materials for thin-film solar cells. Nowadays there are a wide range of earth-abundant absorber materials that have been studied around the world by different research groups. The current thin film photovoltaic market is dominated by technologies based on the use of CdTe and CIGS, these solar cells have been made with laboratory efficiencies up to 19.6% and 20.8% respectively. However, the scarcity and high cost of In, Ga and Te can limit in the long-term the production in large scale of photovoltaic devices. On the other hand, quaternary CZTSSe which contain abundant and inexpensive elements like Cu, Zn, Sn, S and Se has been a potential candidate for PV technology having solar cell efficiency up to 12.6%, however, there are still some challenges that must be accomplished for this material. Therefore, it is evident the need to find the alternative inexpensive and earth abundant materials for thin film solar cells. One of these alternatives is copper antimony sulfide(CuSbS2) which contains abundant and non-toxic elements which has a direct optical band gap of 1.5 eV, the optimum value for an absorber material in solar cells, suggesting this material as one among the new photovoltaic materials. This thesis work focuses on the preparation and characterization of In6Se7, CuSbS2 and CuSb(S1-xSex)2 thin films for their application as absorber material in photovoltaic structures using two stage process by the combination of chemical bath deposition and thermal evaporation.