Ionized cluster beam deposition: Modeling, cluster size measurement and applications

Clusters are aggregations of atoms or molecules, generally intermediate in size between individual atoms and aggregates that are large enough to be called bulk matter. Clusters can also be called nanoparticles, because their size is on the order of nanometers or tens of nanometers. A new field has begun to take shape called nanostructured materials which takes advantage of these atom clusters. The ultra-small size of building blocks leads to dramatically different properties and it is anticipated that such atomically engineered materials will be able to be tailored to perform as no previous material could.^ The idea of ionized cluster beam (ICB) thin film deposition technique was first proposed by Takagi in 1972. It was based upon using a supersonic jet source to produce, ionize and accelerate beams of atomic clusters onto substrates in a vacuum environment. Conditions for formation of cluster beams suitable for thin film deposition have only recently been established following twenty years of effort. Zinc clusters over 1,000 atoms in average size have been synthesized both in our lab and that of Gspann. More recently, other methods of synthesizing clusters and nanoparticles, using different types of cluster sources, have come under development.^ In this work, we studied different aspects of nanoparticle beams. The work includes refinement of a model of the cluster formation mechanism, development of a new real-time, in situ cluster size measurement method, and study of the use of ICB in the fabrication of semiconductor devices.^ The formation process of the vaporized-metal cluster beam was simulated and investigated using classical nucleation theory and one dimensional gas flow equations. Zinc cluster sizes predicted at the nozzle exit are in good quantitative agreement with experimental results in our laboratory.^ A novel in situ real-time mass, energy and velocity measurement apparatus has been designed, built and tested. This small size time-of-flight mass spectrometer is suitable to be used in our cluster deposition systems and does not suffer from problems related to other methods of cluster size measurement like: requirement for specialized ionizing lasers, inductive electrical or electromagnetic coupling, dependency on the assumption of homogeneous nucleation, limits on the size measurement and non real-time capability. Measured ion energies using the electrostatic energy analyzer are in good accordance with values obtained from computer simulation. The velocity (v) is measured by pulsing the cluster beam and measuring the time of delay between the pulse and analyzer output current. The mass of a particle is calculated from m = (2E/v$\sp2).$ The error in the measured value of background gas mass is on the order of 28% of the mass of one N$\sb2$ molecule which is negligible for the measurement of large size clusters. This resolution in cluster size measurement is very acceptable for our purposes.^ Selective area deposition onto conducting patterns overlying insulating substrates was demonstrated using intense, fully-ionized cluster beams. Parameters influencing the selectivity are ion energy, repelling voltage, the ratio of the conductor to insulator dimension, and substrate thickness. ^

Essays on city size distribution and real estate bubbles

This is a dissertation about urban systems; within this broad subject I tackle three issues, one that focuses on an observed inter-city relationship and two that focus on an intra-city phenomenon. In Chapter II I adapt a model of random emergence of economic opportunities from the firm growth literature to the urban dynamics situation and present several predictions for urban system dynamics. One of these predictions is that the older the city the larger and more diversified it is going to be on average, which I proceed to verify empirically using two distinct datasets. In Chapter III I analyze the Residential Real Estate Bubble that took place in Miami-Dade County from 1999 to 2006. I adopt a Spatial-Economic model developed for the Paris Bubble episode of 1984–1993 and formulate an innovative test of the results in terms of speculative intensity on the basis of proxies of investor activity available in my dataset. My results support the idea that the best or more expensive areas are also where the greatest speculative activity takes place and where the rapid increase in prices begins. The most significant departure from previous studies that emerges in my results is the absence of a wider gap between high priced areas and low priced areas in the peak year. I develop a measure of dispersion in value among areas and contrast the Miami-Dade and Paris episodes. In Chapter IV I analyze the impact on tax equity of a Florida tax-limiting legislation known as Save Our Homes. I first compare homesteaded and non-homesteaded properties, and second, look within the subset of homesteaded properties. I find that non-homesteaded properties increase their share of taxes paid relative to homesteaded properties during an up market, but that this is reversed during a down market. For the subset of homesteaded properties I find that the impact on tax equity of SOH will depend on differential growth rates among higher and lower valued homes, but during times of rapid home price appreciation, in a scenario of no differential growth rates in property values, SOH increases progressivity relative to the prior system.

Fluorescence Characteristics of Size-Fractionated Dissolved Organic Matter: Implications for a Molecular Assembly Based Structure?

Surface freshwater samples from Everglades National Park, Florida, were used to investigate the size distributions of natural dissolved organic matter (DOM) and associated fluorescence characteristics along the molecular weight continuum. Samples were fractionated using size exclusion chromatography (SEC) and characterized by spectroscopic means, in particular Excitation-Emission Matrix fluorescence modeled with parallel factor analysis (EEM-PARAFAC). Most of the eight components obtained from PARAFAC modeling were broadly distributed across the DOM molecular weight range, and the optical properties of the eight size fractions for all samples studied were quite consistent among each other. Humic-like components presented a similar distribution in all the samples, with enrichment in the middle molecular weight range. Some variability in the relative distribution of the different humic-like components was observed among the different size fractions and among samples. The protein like fluorescence, although also generally present in all fractions, was more variable but generally enriched in the highest and lowest molecular weight fractions. These observations are in agreement with the hypothesis of a supramolecular structure for DOM, and suggest that DOM fluorescence characteristics may be controlled by molecular assemblies with similar optical properties, distributed along the molecular weight continuum. This study highlights the importance of studying the molecular structure of DOM on a molecular size distribution perspective, which may have important implications in understanding the environmental dynamics such materials.