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No description available.

The high level of molecular control makes the Langmuir-Blodgett (LB) technique an appealing method of film deposition. The uniform nature of the films produced allows convenient investigation of intermolecular interactions and provides information pertaining to the orientation of molecules within films. LB films of two amphiphilic materials with contrasting molecular structures have been deposited. AmPc5 (a metal-free phthalocyanine (pc)) is a two-dimensional, cyclic molecule, whereas AmAzl (a resorcinol calixarene) possesses a three-dimensional basket-type structure. The amphiphilic nature of both molecules is as a result of functional side-chains. The AmPc5 spreading solution was prepared by dissolving in trichloroethane to a concentration of 0.1 mg/ml. After spreading 500-600 ul, the resulting Langmuir film was found to have a critical pressure of 28 mN/m and an area per molecule of 1.61 nm2 on the water surface. Monolayer deposition onto glass substrates enabled spectroscopic examination of the films and comparison to solution spectra. The solution spectrum shows the split Q-band absorption peaks at 700 nm and 733 nm characteristic of metal-free pc's. The LB film spectrum shows a broadening of both peaks and a red shift of the 733 nm peak, and a blue shift of the 700 nm peak. The 700 nm peak is suppressed as a result of the stack-like packing structure of AmPc5. Absorption spectra of floating AmPc5 monolayers imply that the material does not assume the monomer state at any stage of compression. This is characteristic of rigid molecules that induce order within the floating monolayer. The refractive indices (n) and extinction coefficients (k) were determined across the visible wavelength range. Both the n and k values are shown to increase with monolayer thickness, although the n value tends towards a steady value of 2.1. Deposition onto gold coated glass substrates enabled surface plasmon resonance analysis and determination of n and k at specific film thickness'. The n was found to increase with film thickness, tending towards a steady state value of 2.0. This is in excellent agreement with spectroscopic analysis. Absorption spectra measured using polarised light show AmPc5 exhibits dichroism. The calculations indicate that the pc ring lies almost perpendicular to the substrate. AmAzl was dissolved in chloroform to a concentration of 0.5 mg/ml with 10% ethanol to aid solubility. The optimum solution spreading quantity required to form a floating monolayer was found to be between 50 and 100 ul. The film was shown to have a critical pressure of 30 mN/m and an area per molecule of 1.86 nm2 on the water surface. Both LB film and solution spectra show a single absorbance peak at 454 nm which is due to transitions in the azo functional side chains. Calculation of n and k shows that they tend towards steady values of 1.5 and 2.0, respectively. The n obtained via surface plasmon resonance analysis shows a steady state value of 1.43 on silver coated glass and 1.35 on gold coated glass. This suggests a different type of packing structure on all three substrates. The lack of dichroism exhibited by AmAzl indicates the formation of in-plane amorphous films. AmAzl was deposited in alternating layers with tricosenoic acid. The structure was confirmed by X-ray diffraction studies and investigated using second harmonic generation. The second harmonic signal was shown to be proportional to the square of the number of bilayers.

No description available.

No description available.

No description available.

No description available.

Diamond is widely known for its extraordinary properties, such as high hardness, thermal conductivity, electron mobility, energy bandgap and durability making it a very attractive material for many applications. Synthetic diamonds retain most of the attractive properties of natural diamond. Among the types of synthetic diamonds, nanocrystalline diamond (NCD) is being developed for electrical, tribological, optical, and biomedical applications. In this research work, NCD films were grown by the pulsed electron beam ablation (PEBA) method at different process conditions such as accelerating voltage, pulse repetition rate, substrate material and temperature. PEBA is a relatively novel deposition technique, which has been developed to provide researchers with a new means of producing films of equal or better quality than more conventional methods such as Pulsed Laser Deposition, Sputtering, and Cathodic Vacuum Arc. The deposition process parameters have been defined by estimating the temperature and pressure of the plasma particles upon impact with the substrates, and comparing the data with the carbon phase diagram. Film thickness was measured by visible reflectance spectroscopy technique and was in the range of 40 – 230 nm. The nature of chemical bonding, namely, the ratio (sp3/sp3+sp2) and nanocrystallinity percentage were estimated using visible Raman spectroscopy technique. The films prepared from the ablation of a highly ordered pyrolytic graphite (HOPG) target on different substrates consisted mainly of nanocrystalline diamond material in association with a diamond-like carbon phase. The micro-structural properties and surface morphology of the films were studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The mechanical properties of the NCD films were evaluated by nano-indentation.

Atomic vapors condensed onto solid surfaces form a remarkable category of condensed matter materials, the so-called thin films, with a myriad of compositions, morphological structures, and properties. The dynamic process of atomic condensation exhibits self-assembled pattern formation, producing morphologies with atomic-scale three-dimensional structures of seemingly limitless variety. This study attempts to shed new light on the dynamical growth processes of thin film deposition by analyzing in detail a previously unreported specific distinct emergent structure, a crystalline triangular-shaped spike that grows within copper and silver thin films. I explored the deposition parameters that lead to the growth of these unique structures, referred to as ``nanospikes'', fabricating approximately 55 thin films and used scanning electron microscopy and x-ray diffraction analysis. The variation of parameters include: vapor incidence angle, film thickness, substrate temperature, deposition rate, deposition material, substrate, and source-to-substrate distance. Microscopy analysis reveals that the silver and copper films deposited at glancing vapor incidence angles, 80 degrees and greater, have a high degree of branching interconnectivity between adjacent inclined nanorods. Diffraction analysis reveals that the vapor incidence angle influences the sub-populations of crystallites in the films, producing two different [110] crystal texture orientations. I hypothesize that the growth of nanospikes from nanorods is initiated by the stochastic arrival of vapor atoms and photons emitted from the deposition source at small diameter nanorods, and then driven by localized heating from vapor condensation and photon absorption. Restricted heat flow due to nanoscale thermal conduction maintains an elevated local temperature at the nanorod, enhancing adatom diffusion and enabling fast epitaxial crystal growth, leading to the formation and growth of nanospikes. Electron microscopy and x-ray diffraction analysis, and comparisons to related scientific literature, support this hypothesis. I also designed a highly modular ultrahigh vacuum deposition chamber, capable of concurrently mounting several different pieces of deposition equipment, that allows for a high degree of control of the growth dynamics of deposited thin films. I used the newly designed chamber to fabricate tailor-made nanostructured tantalum films for use in ultracapacitors, for the Cabot Corporation. / Thesis (Ph.D, Physics, Engineering Physics and Astronomy) -- Queen's University, 2011-01-17 15:22:47.533

Conjugated polymers have been used in various applications (battery, supercapacitor, electromagnetic shielding, chemical sensor, biosensor, nanocomposite, light-emitting-diode, electrochromic display etc.) due to their excellent conductivity, electrochemical and optical properties, and low cost. Polyaniline has attracted the researchers from all disciplines of science, engineering, and industry due to its redox properties, environmental stability, conductivity, and optical properties. Moreover, it is a polymer with fast electroactive switching and reversible properties displayed at low potential, which is an important feature in many applications. The thin oriented polyaniline films have been fabricated using self-assembly, Langmuir-Blodgett, in-situ self-assembly, layer-by-layer, and electrochemical technique. The focus of this thesis is to synthesize and characterize polyaniline thin films with and without dyes. Also, the purpose of this thesis is to find the fastest electroactive switching PANI electrode in different electrolytic medium by studying their electrochemical properties. These films were fabricated using two deposition techniques: in-situ self-assembly and electrochemical deposition. The characterization of these films was done using techniques such as Fourier Transform Infrared Spectroscopy (FTIR), UV-spectroscopy, Scanning Electron Microscope (SEM), and X-Ray Diffraction (XRD). FTIR and UV-spectroscopy showed similar results in the structure of the polyaniline films. However, for the dye incorporated films, since there was an addition in the synthesis of the material, peak locations shifted, and new peaks corresponding to these materials appeared. The 1 layer PANI showed compact film morphology, comparing to other PANI films, which displayed a fiber-like structure. Finally, the electrochemical properties of these thin films were studied using cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) in different scenarios. These scenarios included the study in different acid based electrolytes and different gel based electrolytes. The ultra-thin self-assembled PANI films were shown to have a faster switching time, especially for the 1 layer PANI, whereas the color contrast could be observed for the film containing the dye molecule. Also, HCl based electrolyte gave the best electrochemical reversibility compared to other acids used. For the gelatin and PVA based electrolytes, having the same concentration, the results were similar. Hence, the change in the electrolyte consistencies, from liquid to semi-solid, did not change the electrochemical properties of the films. Finally, in the EIS, it was shown that these PANI thin films exhibit a pseudo-capacitance behavior, and as the film thickness grew, the capacitance increased.