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Title:Thermal and dynamic processes in deposition, growth, and etching of materials: I. Thermal and collision-induced activation of alkyl intermediates on aluminum. II. Chemical vapor deposition and growth of silicide on copper
Author(s):Lohokare, Shrikant Prabhakar
Doctoral Committee Chair(s):Nuzzo, Ralph G.
Department / Program:Chemical Physics
Discipline:Chemical Physics
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Physical
Engineering, Materials Science
Abstract:Chemical vapor deposition (CVD) is becoming an increasingly important manufacturing process for the fabrication of VLSI and ULSI devices. A major challenge in optimizing a CVD process is developing an understanding of the complex mechanistic pathways followed. The first section in this thesis reports studies on the thermal and dynamical activation of surface bound alkyl species which play a vital role in the form of intermediates in metal-organic chemical vapor deposition. The particular systems of interest are those of aluminum CVD precursors. Models of these intermediates are obtained by thermal decomposition of alkyl iodides. The results provide an insight into the complex reaction patterns involved in the thermal reactions and rate-structure sensitivities of the alkyl species in the presence of the coadsorbed halogen atom. Multiple reaction pathways including metal etching processes which bear direct implications to the synthesis of organometallics and metal etching, are identified.
It is becoming apparent that chemistry at surfaces, whether it be heterogeneous catalysis, semiconductor etching, or chemical vapor deposition, is controlled by much more than the nature and structure of the surface. Also, nonthermal activation of autocatalytic reactions is often required for the nucleation and growth of thin films in devices so that the stability of the device structure is maintained. Dynamical pathways followed in these high pressure and energy processes have to be well understood. The second part of these studies describe an investigation of collision-induced reaction of alkyl intermediates using supersonic inert gas atomic beams. Selective activation of a thermodynamically favored unimolecular decomposition reaction is initiated by hyperthermal collisions. Quantitative estimations of the reaction cross sections are made using straightforward hard sphere energy transfer dynamics. This successful demonstration of collision-induced activation of large, multiatomic moieties has paved the way for proposed studies (now underway in our group) on actual CVD precursors with known barriers to nucleation and growth.
In the second section, the reaction mechanisms and kinetics of competitive dissociation, disproportionation, and thin film growth processes involved in the chemical vapor deposition of metal-silicide thin films are investigated. Metal-silicides are widely used as interconnect and gate materials in devices and also as corrosion resistant materials. Reactivity of silane and disilane with copper is studied in detail using temperature programmed reaction, Auger electron, Fourier transform infrared reflection absorption spectroscopies and low energy electron diffraction. For both the precursors, the structural chemistry and product distributions of adsorbed intermediates found at low temperatures are quite rich but significantly differ at the mechanistic level. It is shown quantitatively that disilane is almost 2-3 orders of magnitude more reactive than silane due to its facile Si-Si bond dissociation. However, in both cases, kinetics of silicon deposition and silicide formation are limited by the site-blocking effect of surface bound hydrogen generated by the decomposition of the silyl fragments. An ordered silicide overlayer is readily formed at higher coverages effected above dihydrogen desorption temperatures. This bimolecular process has to compete with an associative reaction which leads to the formation of silane. The results obtained from the different spectroscopic data show that the growth process involves an intriguing set of coupled reactions in which deposition, island growth, and Si etching effectively compete in a complex manner. Understanding of these parameters and the reaction mechanisms involved, enables the application of this process for the vapor phase growth of silicide thin films.
Issue Date:1996
Rights Information:Copyright 1996 Lohokare, Shrikant Prabhakar
Date Available in IDEALS:2011-05-07
Identifier in Online Catalog:AAI9712360
OCLC Identifier:(UMI)AAI9712360

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