Self-assembled monolayers (SAMs) consist of densely packed long-chain organic molecules, which are chemisorbed on metal substrates through a sulfur head group. The purpose of this work, is to study the arrangement and structure of SAMs by IR, XPS, NEXAFS, STM, Ellipsometry and contact angle. While the first group of triptycenethiols and the second group of triarylaminethiols show a formation of disordered films on the gold surface, the third group of alkanethioacetates shows the formation of highly ordered monolayers. A further adsorption to upright oriented molecules is hindered due to...