Self-assembled monolayers at/on metal surfaces in contact with electrolyte solutions – i.e. on electrode surfaces – can be studied with numerous spectroscopic, topographic (surface-structure-sensitive) and electrochemical methods. Structural, kinetic and energetic aspects may be elucidated to get a complete picture of formation, structure and properties of the formed SAM. A rough estimate of the degree of coverage ca be obtained from electrochemical measurements (cyclic voltammetry) performed after different times of exposure of the surface to be coated to the solution containing the SAM-forming species. In case of a two-step formation mechanism (adsorption in irregular arrangement first, self-organisation following) the data provide only an overall picture not specific to the degree of ordering. Spectroscopic methods employed preferably in situ provide molecular-level information about the adsorbate, its interaction with the electrode surface and its environment and changes effected by adsorption and self-assembly. Spatial arrangement of molecules can be observed preferably with scanning probe methods, in particular with atomic force microscopy. Tools covered in this talk include electrochemical, spectroscopic and surface-sensitive ones. Methods within these groups include those sensitive to degree of coverage, structure of molecular adsorbate, mode of adsorbate-surface interaction, and degree of ordering

• R. Holze: Landolt-Börnstein: Numerical Data and Functional Relationships in Science and Technology, New Series, Group IV: Physical Chemistry, Volume 9: Electrochemistry, Subvolume A: Electrochemical Thermodynamics and Kinetics, W. Martienssen, M.D. Lechner, Eds., Springer-Verlag, Berlin 2007
• R. Holze: Surface and Interface Analysis: An Electrochemists Toolbox, Springer-Verlag, Heidelberg, 2009