This dissertation investigates a new method for the growth of morphologically flat, epitaxial metal films on single crystal metal substrates. This research is based on the concept of monolayer surface modification assisted by galvanic displacement, utilizing successive potential controlled and electroless deposition steps. The growth of silver thin films on gold single crystal substrate is examined.; In the first part of this study, factors associated with the stability of an underpotentially deposited layer at open circuit potential are quantitatively considered and mathematically modeled. Classical electrochemical tools such as cyclic voltammetry, chronopotentiometry and chronoamperometry are used to investigate the stability of an underpotentially deposited layer at open circuit potential. Simple modeling based on the Lorentzian cumulative function is used to fit the behavior of the underpotentially deposited layer at open circuit potential.; In the second part, electrochemical methods and ex-situ surface characterization techniques (scanning tunneling microscopy, x-ray photoelectron spectroscopy and x-ray diffraction) are employed for studying the growth kinetics of layers. Replacement schedules are optimized with respect to sacrificial layer identity (Tl, Pb or Bi), specific polarization regimes and rate of deposition in order to yield a working protocol for growth of crystallographically well-defined, morphologically flat and inclusion-free thin metal films on single crystal substrates.; The unique nature of the newly developed method (one that combines potential controlled and electroless steps within a single deposition event), is the major result of the work. Epitaxial growth by monolayer restricted galvanic displacement, with its unique ability to provide maximum growth uniformity with minimum external control, is superior to the existing electrodeposition techniques.
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