Reliability of micro- and nanodevices, as well as magnetic storage devices require the use of lubricant films for the protection of sliding surfaces. To minimize high adhesion, friction, and because of small clearances in the devices, these films should be molecularly thick. Liquid films of low surface tension or certain hydrophobic solid films can be used. Ordered molecular assemblies with high hydrophobicity can be engineered using chemical grafting of various polymer molecules with suitable functional head groups, spacer chains and nonpolar surface terminal groups.
The classical approach to lubrication uses multi-molecular layers of liquid lubricants. Boundary lubricant films are formed by either physisorption, chemisorption, or chemical reaction. The physiosorbed films can be either monomolecularly or polymolecularly thick. The chemisorbed films are monomolecular, but stoichiometric films formed by chemical reaction can be multilayered. A good boundary lubricant should have a high degree of interaction between its molecules and the sliding surface. As a general rule, liquids are good lubricants when they are polar and thus able to grip on solid surfaces (or be adsorbed).
In this chapter, we focus on self-assembled monolayers (SAMs) for high hydrophobicity and/or low adhesion, friction, and wear. SAMs are produced by various organic precursors. We first present a primer to organic chemistry followed by an overview on suitable substrates, head groups, spacer chains, and end groups in the molecular chains and an overview of tribological properties of SAMs. The adhesion, friction, and wear properties of SAMs, having alkyl and biphenyl spacer chains with different surface terminal and head groups, are surveyed. The friction data are explained using a molecular spring model in which the local stiffness and intermolecular force govern its frictional performance. Based on the nanotribological studies of SAM films by AFM, they exhibit attractive hydrophobic and tribological properties.