Advanced SPM studies on the growth of ultrathin films of organic semiconductors at metal and dielectric interfaces

Many studies on the morphology, molecular orientation, device performance, substrate nature and growth parameter dependence have been carried out since the proposal of Sexithiophene (6T) for organic electronics [ ] However, these studies were mostly performed on films thicker than 20nm and without specifically addressing the relationship between morphology and molecular orientation within the nano and micro structures of ultrathin films of 0-3 monolayers. In 2004, the observation that in OFETs only the first few monolayers at the interface in contact with the gate insulator contribute to the charge transport [ ], underlined the importance to study submonolayer films and their evolution up to a few monolayers of thickness with appropriate experimental techniques. We present here a detailed Non-contact Atomic Force Microscopy and Scanning Tunneling Microscopy study on various substrates aiming at the investigation of growth mechanisms. Most reported similar studies are performed on ideal metals in UHV. However it is important to investigate the details of organic film growth on less ideal and even technological surfaces and device testpatterns. The present work addresses the growth of ultra thin organic films in-situ and quasi real-time by NC-AFM. An organic effusion cell is installed to evaporate the organic material directly onto the SPM sample scanning stage.

Fluorescence close to dielectric interfaces

The aim of the work was to study the correlation between the orientation and excited-state lifetimes of organic dyes close to dielectric interfaces. For this purpose, an experimental setup was designed and built, guiding the light through a prism in total internal reflection geometry. Fluorescence intensities and lifetimes for an ensemble of dye molecules were analyzed as a function of the excitation and detection polarizations. Working close to the total internal reflection angle, the differences between polarization combinations were enhanced. A classical electromagnetic model that assumes a chromophore as a couple of point-like electrical dipoles was developed. A numerical method to calculate the excitation and emission of dye molecules embedded in a multilayer system was implemented, by which full simulation of the time resolved fluorescence experiments was achieved. Free organic dyes and organic dyes covalently bound to polyelectrolyte chains were used. The polymer functionalization process avoided aggregation and provided control over the dyes position, within a few nanometers to the interface. Moreover, by varying the pH, the polymer chains could be deposited on different substrates with different conformations and the resulting fluorescence characteristics analyzed. Initially the fluorescence of organic dyes embedded in a polymer matrix was studied as a function of the distance between the fluorophores and the polymer-air interface. The non-radiative decay rate, vacuum decay rate and the relative angle between the excitation and emission dipoles of the chromophores could be determined. Different free organic dyes were deposited onto different dielectric spacers, as close as possible to the air-dielectric interface. Surprisingly, the fluorescence characteristics of dyes deposited onto polyelectrolyte layer were in good agreement with theoretical predictions of dyes in a polymer matrix, even when the layer was only 2 nm thick. When functionalized chains were deposited at low pH, on top of a polyelectrolyte spacer, the fluorescence had the characteristics of emitters embedded in a polymer matrix as well. Surface deposition at high pH showed an intermediate behaviour between emitters embedded in polymer and on top of the surface, in air. In general, for low pH values, the chains are deposited on a substrate in a train-like conformation. For high pH values, the chains are deposited in a loop-like conformation. As a consequence at low pH the functionalized polymer strongly interdigitates with the polyelectrolyte chains of the spacer, bringing most of the dyes inside the polymer. Thus, the fluorophores may experience the polymer as surrounding environment. On the other hand, for high pH values the dye-loaded chains adsorbed have a conformational arrangement of dense loops that extend away from the surface. Therefore many fluorophores experience the air as surrounding environment. Changing the spacer from polyelectrolyte to negatively charged silane produced contradictory results for lifetimes and intensities. The fluorescence intensities indicated the behaviour of emitters embedded in a polymer matrix, regardless of the pH value. On the other hand, for low pH values, the excited-state lifetimes showed that the emitters behaved as in air. For higher pH values, an intermediate behaviour between fluorophores located within and above of a dielectric film was observed. The poor agreement between theoretical and experimental data may be due to the simplified model utilized, by which the dipoles are assumed either in one side or in the other with respect to a geometrical air-dielectric interface. In the case when the dielectric film is constituted by the functionalized polymer chains themselves, reality is more complex and a different model may apply. Nevertheless, possible applications of the technique arise from a qualitative analysis.

Design. Fabrication and Characterization of Fiber Optic Sensors for Physical and Chemical Applications

Advent of lasers together with the advancement in fiber optics technology has revolutionized the sensor technology. Advancement in the telemetric applications of optical fiber based measurements is an added bonus. The present thesis describes variety of fiber based sensors using techniques like micro bending, long period grating and evanescent waves. Sensors to measure various physical and chemical parameters are described in this thesis.

Análise de onda completa de superfície seletiva em freqüência do tipo anteparo duplo

This work presents a theoretical analysis and numerical and experimental results of the scattering characteristics of frequency selective surfaces, using elements of type patch perfectly conductor. The structures are composed of two frequency selective surfaces on isotropic dielectric substrates cascaded, separated by a layer of air. The analysis is performed using the method of equivalent transmission line in combination with the Galerkin method, to determine the transmission and reflection characteristics of the structures analyzed. Specifically, the analysis uses the impedance method, which models the structure by an equivalent circuit, and applies the theory of transmission lines to determine the dyadic Green's function for the cascade structure. This function relates the incident field and surface current densities. These fields are determined algebraically by means of potential incidents and the imposition of the continuity of the fields in the dielectric interfaces. The Galerkin method is applied to the numerical determination of the unknown weight coefficients and hence the unknown densities of surface currents, which are expanded in terms of known basis functions multiplied by these weight coefficients. From the determination of these functions, it becomes possible to obtain numerical scattered fields at the top and bottom of the structures and characteristics of transmission and reflection of these structures. At work, we present numerical and experimental results for the characteristics of transmission and reflection. Comparisons were made with other results presented in literature, and it was observed a good agreement in the cases presented suggestions continuity of the work are presented

Método dinâmico aplicado para antenas cilíndricas

Nowadays there has been a major breakthrough in the aerospace area, with regard to rocket launches to research, experiments, telemetry system, remote sensing, radar system (tracking and monitoring), satellite communications system and insertion of satellites in orbit. This work aims at the application of a circular cylindrical microstrip antenna, ring type, and other cylindrical rectangular in structure of a rocket or missile to obtain telemetry data, operating in the range of 2 to 4 GHz, in S-band. Throughout this was developed just the theoretical analysis of the Transverse transmission line method which is a method of rigorous analysis in spectral domain, for use in rockets and missiles. This analyzes the spread in the direction "ρ" , transverse to dielectric interfaces "z" and "φ", for cylindrical coordinates, thus taking the general equations of electromagnetic fields in function of e [1]. It is worth mentioning that in order to obtain results, simulations and analysis of the structure under study was used HFSS program (High Frequency Structural Simulator) that uses the finite element method. With the theory developed computational resources were used to obtain the numerical calculations, using Fortran Power Station, Scilab and Wolfram Mathematica ®. The prototype was built using, as a substrate, the ULTRALAM ® 3850, of Rogers Corporation, and an aluminum plate as a cylindrical structure used to support. The agreement between the measured and simulated results validate the established processes. Conclusions and suggestions are presented for continuing this work

Tight-Binding Approximations in 1D and 2D Coupled-Cavity Photonic Crystal Structures

Light confinement and controlling an optical field has numerous applications in the field of telecommunications for optical signals processing. When the wavelength of the electromagnetic field is on the order of the period of a photonic microstructure, the field undergoes reflection, refraction, and coherent scattering. This produces photonic bandgaps, forbidden frequency regions or spectral stop bands where light cannot exist. Dielectric perturbations that break the perfect periodicity of these structures produce what is analogous to an impurity state in the bandgap of a semiconductor. The defect modes that exist at discrete frequencies within the photonic bandgap are spatially localized about the cavity-defects in the photonic crystal. In this thesis the properties of two tight-binding approximations (TBAs) are investigated in one-dimensional and two-dimensional coupled-cavity photonic crystal structures We require an efficient and simple approach that ensures the continuity of the electromagnetic field across dielectric interfaces in complex structures. In this thesis we develop \textrm{E} -- and \textrm{D} --TBAs to calculate the modes in finite 1D and 2D two-defect coupled-cavity photonic crystal structures. In the \textrm{E} -- and \textrm{D} --TBAs we expand the coupled-cavity \overrightarrow{E} --modes in terms of the individual \overrightarrow{E} -- and \overrightarrow{D} --modes, respectively. We investigate the dependence of the defect modes, their frequencies and quality factors on the relative placement of the defects in the photonic crystal structures. We then elucidate the differences between the two TBA formulations, and describe the conditions under which these formulations may be more robust when encountering a dielectric perturbation. Our 1D analysis showed that the 1D modes were sensitive to the structure geometry. The antisymmetric \textrm{D} mode amplitudes show that the \textrm{D} --TBA did not capture the correct (tangential \overrightarrow{E} --field) boundary conditions. However, the \textrm{D} --TBA did not yield significantly poorer results compared to the \textrm{E} --TBA. Our 2D analysis reveals that the \textrm{E} -- and \textrm{D} --TBAs produced nearly identical mode profiles for every structure. Plots of the relative difference between the \textrm{E} and \textrm{D} mode amplitudes show that the \textrm{D} --TBA did capture the correct (normal \overrightarrow{E} --field) boundary conditions. We found that the 2D TBA CC mode calculations were 125-150 times faster than an FDTD calculation for the same two-defect PCS. Notwithstanding this efficiency, the appropriateness of either TBA was found to depend on the geometry of the structure and the mode(s), i.e. whether or not the mode has a large normal or tangential component.

Near-field coupling and resonant cavity modes in plasmonic nanorod metamaterials

Plasmonic resonant cavities are capable of confining light at the nanoscale, resulting in both enhanced local electromagnetic fields and lower mode volumes. However, conventional plasmonic resonant cavities possess large Ohmic losses at metal-dielectric interfaces. Plasmonic near-field coupling plays a key role in a design of photonic components based on the resonant cavities because of the possibility to reduce losses. Here, we study the plasmonic near-field coupling in the silver nanorod metamaterials treated as resonant nanostructured optical cavities. Reflectance measurements reveal the existence of multiple resonance modes of the nanorod metamaterials, which is consistent with our theoretical analysis. Furthermore, our numerical simulations show that the electric field at the longitudinal resonances forms standing waves in the nanocavities due to the near-field coupling between the adjacent nanorods, and a new hybrid mode emerges due to a coupling between nanorods and a gold-film substrate. We demonstrate that this coupling can be controlled by changing the gap between the silver nanorod array and gold substrate.

Tight-Binding Approximations in 1D and 2D Coupled-Cavity Photonic Crystal Structures

Light confinement and controlling an optical field has numerous applications in the field of telecommunications for optical signals processing. When the wavelength of the electromagnetic field is on the order of the period of a photonic microstructure, the field undergoes reflection, refraction, and coherent scattering. This produces photonic bandgaps, forbidden frequency regions or spectral stop bands where light cannot exist. Dielectric perturbations that break the perfect periodicity of these structures produce what is analogous to an impurity state in the bandgap of a semiconductor. The defect modes that exist at discrete frequencies within the photonic bandgap are spatially localized about the cavity-defects in the photonic crystal. In this thesis the properties of two tight-binding approximations (TBAs) are investigated in one-dimensional and two-dimensional coupled-cavity photonic crystal structures We require an efficient and simple approach that ensures the continuity of the electromagnetic field across dielectric interfaces in complex structures. In this thesis we develop \textrm{E} -- and \textrm{D} --TBAs to calculate the modes in finite 1D and 2D two-defect coupled-cavity photonic crystal structures. In the \textrm{E} -- and \textrm{D} --TBAs we expand the coupled-cavity \overrightarrow{E} --modes in terms of the individual \overrightarrow{E} -- and \overrightarrow{D} --modes, respectively. We investigate the dependence of the defect modes, their frequencies and quality factors on the relative placement of the defects in the photonic crystal structures. We then elucidate the differences between the two TBA formulations, and describe the conditions under which these formulations may be more robust when encountering a dielectric perturbation. Our 1D analysis showed that the 1D modes were sensitive to the structure geometry. The antisymmetric \textrm{D} mode amplitudes show that the \textrm{D} --TBA did not capture the correct (tangential \overrightarrow{E} --field) boundary conditions. However, the \textrm{D} --TBA did not yield significantly poorer results compared to the \textrm{E} --TBA. Our 2D analysis reveals that the \textrm{E} -- and \textrm{D} --TBAs produced nearly identical mode profiles for every structure. Plots of the relative difference between the \textrm{E} and \textrm{D} mode amplitudes show that the \textrm{D} --TBA did capture the correct (normal \overrightarrow{E} --field) boundary conditions. We found that the 2D TBA CC mode calculations were 125-150 times faster than an FDTD calculation for the same two-defect PCS. Notwithstanding this efficiency, the appropriateness of either TBA was found to depend on the geometry of the structure and the mode(s), i.e. whether or not the mode has a large normal or tangential component.

Subwavelength imaging with two symmetrical interfaces by dielectric-tube photonic crystals

As distinct from coated photonic crystals, in this paper we propose a novel one that is made of dielectric tubes arranged in a close-packet square lattice. Without metallic cores, this structure is low-loss and convenient to fabricate. A left-handed frequency region is found in the second band by dispersion characteristic analysis. Without inactive modes for the transverse electric mode, negative refraction and subwavelength imaging are demonstrated by the finite-difference time-domain simulations with two symmetrical interfaces, i.e. Gamma X and Gamma M.

Low temperature surface nitridation processes for dielectric-Ge interfaces

Germanium MOS capacitors have been fabricated with a high-? HfO dielectric using ALD. An in-situ low temperature (250°C) nitrogen plasma treatment on the germanium surface prior to the deposition of HfO was found to be beneficial to the electrical properties of the devices. Germanium MOS capacitors have also been fabricated with a SiO dielectric deposited by an atmospheric pressure CVD 'silox' process. The same low temperature plasma nitridation was found to degrade the electrical properties of the silox devices. The effect of a post-metal anneal in H and N on both types of capacitor structure was also found to degrade device electrical properties. copyright The Electrochemical Society.

A Dielectric Model of Self-Assembled Monolayer Interfaces by Capacitive Spectroscopy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Silica nanoparticles treated by cold atmospheric-pressure plasmas improve the dielectric performance of organic–inorganic nanocomposites

We report on the application of cold atmospheric-pressure plasmas to modify silica nanoparticles to enhance their compatibility with polymer matrices. Thermally nonequilibrium atmospheric-pressure plasma is generated by a high-voltage radio frequency power source operated in the capacitively coupled mode with helium as the working gas. Compared to the pure polymer and the polymer nanocomposites with untreated SiO2, the plasma-treated SiO2–polymer nanocomposites show higher dielectric breakdown strength and extended endurance under a constant electrical stress. These improvements are attributed to the stronger interactions between the SiO2 nanoparticles and the surrounding polymer matrix after the plasma treatment. Our method is generic and can be used in the production of high-performance organic–inorganic functional nanocomposites.

Nanosphere monolayer-templated, ion-assisted nanofeature etching in dielectric materials : a numerical simulation of nanoscale ion flux topography

The results of numerical simulations of nanometer precision distributions of microscopic ion fluxes in ion-assisted etching of nanoscale features on the surfaces of dielectric materials using a self-assembled monolayer of spherical nanoparticles as a mask are presented. It is shown that the ion fluxes to the substrate and nanosphere surfaces can be effectively controlled by the plasma parameters and the external bias applied to the substrate. By proper adjustment of these parameters, the ion flux can be focused onto the areas uncovered by the nanospheres. Under certain conditions, the ion flux distributions feature sophisticated hexagonal patterns, which may lead to very different nanofeature etching profiles. The results presented are generic and suggest viable ways to overcome some of the limitations of the existing plasma-assisted nanolithography.