The Electrostatic Self-Assembly (ESA) technique possesses great advantages over traditional thin film fabrication methods, making it an excellent choice for a number of applications in the fields of linear and nonlinear optics, electronics, sensing and surface coatings. The feasibility of fabricating linear optical interference filters by ESA methods is demonstrated in this thesis work. Basic single-anion/single-cation ESA films are synthesized and their optical parameters -- refractive index and average thickness for individual bilayer -- are investigated to provide a basis for the in-depth design of optical filters. High performance dielectric stack filters and narrowband and wideband antireflection coatings are designed using TFCalc simulation software and are fabricated by ESA. Both bulk film sensitivity and layer sensitivity to manufacturing errors are provided. The significant agreement between simulation and experiment demonstrates the strong capability of ESA to precisely control the refractive index and produce excellent thin film filters. The performance of optical thin film filters is largely enhanced compared to the results of previous methods. The experiment results indicate that the ESA process may be used to fabricate optical filters and other optical structures that require precise index profile control. / Master of Science

Thin film optical filters are made by depositing thin films of optical materials on a substrate in such a way as to produce the required optical and mechanical properties. The Electrostatic Self Assembly (ESA) process is accomplished by the alternate adsorption of poly-anionic and poly-cationic molecules on progressive oppositely charged surfaces. This technique offers several advantages such as ease of fabrication, molecular level uniformity, stable multilayer synthesis and avoidance of the need for a vacuum environment. The ESA process offers an excellent choice for manufacturing optical thin film coatings due to its capability to incorporate multiple properties into films at the molecular level and its ability to be a fast and inexpensive process. The ESA process, as a method for manufacturing optical thin film filters has been investigated in detail in this thesis. A specific design was made and analyzed using TFCalc, a commercial thin film design software. Sensitivity analysis detailing the changes in filter response to errors in thickness and refractive index produced by the ESA process were done. These proved that with a high level of quality control, highly reliable and accurate optical thin films can be made by the ESA process. / Master of Science

This dissertation demonstrates the feasibility of using novel electrostatic self-assembly (ESA) methods to fabricate linear and nonlinear optical thin films and components. The ESA process involves the layer-by-layer alternate adsorption of anionic and cationic complexes from aqueous solutions. Selection of the molecules in each layer, their orientation at the molecular level, and the order in which the layers are assembled determine the film's bulk optical, electronic, magnetic, thermal, mechanical and other properties. In this work, the capability of nanoscale control over film optical properties allowed the fabrication of complicated refractive index profiles required for linear optical interference filters. The inherent ordered nature of ESA films yielded extremely stable noncentrosymmetric thin films for second-order nonlinear optical applications. The ESA technique offers numerous advantages over conventional thin film fabrication methods and offers great potential in commercial applications such as reflectance and AR filters, EO waveguides and modulators and other optoelectronic devices. The structure of each monolayer in ESA films is dependent on the processing parameters, producing subsequent variations in bulk film properties both intentionally and incidentally. As this method is still in its infancy, variations in ESA processing methods, including process automation, are considered first in this document. These results allowed carefully controlled refractive index experiments and the synthesis of both step and graded index structures, several microns thick. Dielectric stack, Rugate, and antireflection optical interference filters were designed, synthesized and demonstrated. c(2) films of both commercially available polymer dyes and novel polymers designed specifically for the ESA process were demonstrated using second harmonic generation. UV/vis spectroscopy, ellipsometry and atomic force microscopy analysis are presented. / Ph. D.

Metal-insulator-metal (MIM) capacitors are used for analog, RF, and DRAM applications in ICs. The International Technology Roadmap for Semiconductors (ITRS) specifies continuing increase in capacitance density (> 7 fF/ m2), lower leakage current density (< 10 8 A/cm2), very low effective oxide thickness (EOT < 1 nm, for DRAM applications), and better capacitance density-voltage (C-V) linearity ( < 100 ppm/V2, for analog/RF applications). In addition, the maximum fabrication/processing temper-ature should not be greater than 400 0C, in order to be compatible with the thermal budget of back-end fabrication steps. Low dielectric constants of conventional SiO2 and Si3N4 capacitors limit the capacitance densities of these devices. Although scaling down of dielectric thickness increases the capacitance density, it results in large leakage current density and poor C-V linearity. In this work, the effects of high-k materials (Eu2O3, Gd2O3, TiO2) on the device performance of MIM capacitors are studied. The performance of multi-dielectric stack, and doped-dielectric stack devices are also investigated. The effects of anneal temperature, anneal ambient, anneal mode, and dielectric thickness on device performance are evaluated. C-V, current density-voltage (J-V), and reliability measurements are performed to benchmark the electrical performance, and this is correlated to the structural and material properties of the films through ellipsometry, scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) measurements. High-performance MIM capacitors are fabricated by using (RF sputtered) Eu2O3 dielectric. The fabricated devices are subjected to different anneal conditions, to study their device performance. Forming gas (FG) and argon (Ar) annealed devices are shown to have higher capacitance densities (7 fF/ m2jF G), lower leakage current densities (3.2 10 8 A/cm2jAr at -1 V), and higher , compared to oxygen (O2) annealed de-vices ( 100kHz = 193 ppm/V2jO2). The electrical characterization results are correlated with the surface chemical states of the films through XPS measurements. The annealing ambient is shown to alter the surface chemical states, which, in turn, modulate the electrical characteristics. High-density MIM capacitors are fabricated by using (RF sputtered) Gd2O3, and Gd2O3-Eu2O3 stacked dielectrics. The fabricated Gd2O3 capacitors are also subjected to different anneal conditions, to study their device performance. Although Gd2O3 capacitors provide high capacitance density (15 fF/ m2), they suffer from high leakage current density, high , and poor reliability. Therefore, stacked dielectrics of Gd2O3 and Eu2O3 (Gd2O3/Eu2O3 and Eu2O3/Gd2O3) are fabricated to reduce leakage current density, improve , and improve reliability, with only a marginal reduction in capacitance density, compared to Gd2O3 capacitors. Density of defects and barrier/trap heights are extracted for the fabricated capacitors, and correlated with the device characteristics. High-performance MIM capacitors with bilayer dielectric stacks of (ALD-deposited) TiO2-ZrO2, and Si-doped ZrO2 are characterized. Devices with (ALD-deposited) TiO2/ ZrO2/TiO2 (TZT) and AlO-doped TZT stacks are also characterized. The influence of doping on the device performance is studied. The surface chemical states of the deposited films are analyzed by high-resolution XPS. The structural analysis of the samples is performed by XRD measurements, and this is correlated to the electrical characteristics of the devices. Reliability measurements are performed to study the effects of constant voltage and current stress on device performance. High capacitance density (> 45 fF/ m2), low leakage current density (< 5 10 8 A/cm2 at -1 V, for most devices), and sub-nm EOT are achieved. These parameters exceed the ITRS specifications for DRAM storage capacitors.