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. ^

Influence of the sputtering flow regime on the structural properties and magnetic behavior of Fe-Ga thin films (Ga ∼ 30 at.%)

In this paper we analyze the structure of Fe-Ga layers with a Ga content of ∼30 at.% deposited by the sputtering technique under two different regimes. We also studied the correlation between the structure and magnetic behavior of the samples. Keeping the Ar pressure fixed, we modified the flow regime from ballistic to diffusive by increasing the distance between the target and the substrate. X-ray diffraction measurements have shown a lower structural quality when growing in the diffusive flow. We investigated the impact of the growth regime by means of x-ray absorption fine structure (XAFS) measurements and obtained signs of its influence on the local atomic order. Full multiple scattering and finite difference calculations based on XAFS measurements point to a more relevant presence of a disordered A2 phase and of orthorhombic Ga clusters on the Fe-Ga alloy deposited under a diffusive regime; however, in the ballistic sample, a higher presence of D0_3/B2 phases is evidenced. Structural characteristics, from local to long range, seem to determine the magnetic behavior of the layers. Whereas a clear in-plane magnetic anisotropy is observed in the film deposited under ballistic flow, the diffusive sample is magnetically isotropic. Therefore, our experimental results provide evidence of a correlation between flow regime and structural properties and its impact on the magnetic behavior of a rather unexplored compositional region of Fe-Ga compounds.

Piezoresponse force microscopy investigations of Aurivillius phase thin films

The sol-gel synthesis and characterization of n≥3n≥3 Aurivillius phase thin filmsdeposited on Pt/Ti/SiO2–SiPt/Ti/SiO2–Si substrates is described. The number of perovskite layers, nn, was increased by inserting BiFeO3BiFeO3 into three layered Aurivillius phase Bi4Ti3O12Bi4Ti3O12 to form compounds such as Bi5FeTi3O15Bi5FeTi3O15 (n=4)(n=4). 30% of the Fe3+Fe3+ ions in Bi5FeTi3O15Bi5FeTi3O15 were substituted with Mn3+Mn3+ ions to form the structureBi5Ti3Fe0.7Mn0.3O15Bi5Ti3Fe0.7Mn0.3O15. The electromechanical responses of the materials were investigated using piezoresponse force microscopy and the results are discussed in relation to the crystallinity of the films as measured by x-ray diffraction.

Study of the kinetics and mechanism of rapid self-assembly in block copolymer thin films during solvo-microwave annealing

Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high- lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during "solvo-microwave" annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 degrees C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during "solvo-microwave" annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O-2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.

Less strain, more gain_nano_patterning III-N thin films

Controlling the growth mechanism for nano-structures is one of the most critical topics in material science. In the past 10 years there has been intensive research worldwide in IIIN based nanowires for its many unique photonic and electrical properties at this scale. There are several advantages to nanostructuring III-N materials, including increased light extraction, increased device efficiency, reduction of efficiency droop, and reduction in crystallographic defect density. High defect densities that normally plague III-N materials and reduce the device efficiency are not an issue for nano-structured devices such as LEDs, due to the effective strain relaxation. Additionally regions of the light spectrum such as green and yellow, once found difficult to achieve in bulk planar LEDs, can be produced by manipulating the confinement and crystal facet growth directions of the active regions. A cheap and easily repeatable self-assembly nano-patterning technique at wafer scale was designed during this thesis for top down production of III-N nanowires. Through annealing under ammonia and N2 gas flow, the first reported dislocation defect bending was observed in III-N nanorods by in-situ transmission electron microscopy heating. By growing on these etched top down nanorods as a template, ultra-dense nanowires with apex tipped semi-polar tops were produced. The uniform spacing of 5nm between each wire is the highest reported space-filling factor at 98%. Finally by using these ultra-dense nanorods bridging the green gap of the light spectrum was possible, producing the first reported red, yellow, green light emission from a single nano-tip.

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.

Competing anisotropies in exchange biased nano-structured thin films

The magnetic anisotropies of a patterned, exchange biased Fe50Mn50/Ni80Fe20 system are studied using ferromagnetic resonance, supplemented by Brillouin light scattering experiments and Kerr magnetometry. The exchange biased bi-layer is partially etched into an antidot geometry so that the system approximates a Ni80 Fe20 layer in contact with antidot structured Fe50 Mn50 . Brillouin light scattering measurements of the spin wave frequency dependence on the wave vector reveal a magnonic band gap as expected for a periodic modulation of the magnetic properties. Analysis of the ferromagnetic resonance spectra reveals 8-fold and 4-fold contributions to the magnetic anisotropy. Additionally, the antidot patterning decreases the magnitude of the exchange bias and modifies strongly its angular dependence. Softening of all resonance modes is most pronounced for the applied magnetic field aligned within 10◦ of the antidot axis, in the direction of the bias. Given the degree to which one can tailor the ground state, the resulting asymmetry at low frequencies could make this an interesting candidate for applications such as selective/directional microwave filtering and multi-state magnetic logic.

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.

Few-layer, large-area, 2D covalent organic framework semiconductor thin films.

In this work, we synthesize large-area thin films of a conjugated, imine-based, two-dimensional covalent organic framework at the solution/air interface. Thicknesses between ∼2-200 nm are achieved. Films can be transferred to any desired substrate by lifting from underneath, enabling their use as the semiconducting active layer in field-effect transistors.

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.

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.