Date of Completion


Embargo Period



Self-assembled monolayers, surfaces, interfaces, density functional theory

Major Advisor

Rampi Ramprasad

Associate Advisor

S. Pamir Alpay

Associate Advisor

George A. Rossetti, Jr.

Field of Study

Materials Science and Engineering


Doctor of Philosophy

Open Access

Campus Access


Self-assembled monolayers (SAMs) are highly ordered molecular assemblies placed on surfaces or at interfaces to tune various properties through the adequate choice and conformation of the SAM. In the last decades, SAMs have played an important role in the development of technological devices such as organic light-emitting diodes, photovoltaics and field-effect transistors. This broad applicability is possible through the control of different factors, including SAM surface coverage, binding modes, structure and chemical composition. However, the specific effect of the individual factors on the tunability of surface/interface properties is still a subject of study. In this thesis, density functional theory was used to predict the effect of SAMs on the mechanical and electronic properties of surfaces and interfaces. The geometry, molecular coverage, binding mode, stability, adhesion and work function of surface-SAMs and interface-SAMs were studied. In addition, first principles thermodynamics was used to determine the effect of the environmental conditions on the properties of metal-metal oxide and metal-SAM-metal oxide heterostructures. The results reported in this thesis were compared with parallel experimental work developed by our collaborators in the Rensselaer Polytechnic Institute and also with available data in the literature. It is anticipated that this work will lead to design guidelines for the system- and applicationspecific choice of SAMs.