Chemical and Biomolecular Engineering Theses and Dissertations
Permanent URI for this collectionhttp://hdl.handle.net/1903/2751
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Item REACTION NETWORK ANALYSIS FOR THIN FILM DEPOSITION PROCESSES(2016) Ramakrishnasubramanian, Krishnaprasath; Adomaitis, Raymond; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Understanding the growth of thin films produced by Atomic Layer Deposition (ALD) and Chemical Vapor Deposition (CVD) has been one of the most important challenge for surface chemists over the last two to three decades. There has been a lack of complete understanding of the surface chemistry behind these systems due to the dearth of experimental reaction kinetics data available. The data that do exist are generally derived through quantum computations. Thus, it becomes ever so important to develop a deposition model which not only predicts the bulk film chemistry but also explains its self-limiting nature and growth surface stability without the use of reaction rate data. The reaction network analysis tools developed in this thesis are based on a reaction factorization approach that aims to decouple the reaction rates by accounting for the chemical species surface balance dynamic equations. This process eliminates the redundant dynamic modes and identifies conserved modes as reaction invariants. The analysis of these invariants is carried out using a Species-Reaction (S-R) graph approach which also serves to simplify the representation of the complex reaction network. The S-R graph is self explanatory and consistent for all systems. The invariants can be easily extracted from the S-R graph by following a set of straightforward rules and this is demonstrated for the CVD of gallium nitride and the ALD of gallium arsenide. We propose that understanding invariants through these S-R graphs not only provides us with the physical significance of conserved modes but also give us a better insight into the deposition mechanism.Item Combinatorial Experiments Using a Spatially Programmable Chemical Vapor Deposition System(2007-05-02) Sreenvivasan, Ramaswamy; Adomaitis, Raymond; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)A CVD reactor concept featuring a segmented design allows individual regions of a wafer to be exposed to different precursor concentrations simultaneously during a run resulting in different thickness profiles on the wafer and a thickness gradient at the boundaries between segment regions. Different recipes were cycled through each of the segments in a sequence of deposition experiments to develop a model relating precursor concentration to film thickness in each segment region. As a demonstration of spatial programmability, the system was re-programmed using this model to produce uniform thickness amongst the segments; inter-segment uniformity approaching 0.48 % (thickness standard deviation) was demonstrated. In a subsequent study, segmented CVD reactor designs enabling spatial control of across-wafer gas phase composition were evaluated for depositing graded films suitable for combinatorial studies. Specifically two reactor designs were evaluated with experiments and response surface model (RSM) based analysis to quantify the reactor performance in terms of film thickness uniformity, sensitivity to adjustable reactor operating conditions, range of thickness over which uniformity could be achieved and each reactor's ability to control the thickness gradient across the wafer surface. Design features distinguishing the two reactor systems and their influence on gradient control versus deposition rate performance are summarized. Response Surface (RS) models relating wafer state properties to process recipes are shown to be effective tools to quantify, qualify and compare different reactor designs.