The thicknesses of SAMs can be measured using ellipsometry and X-ray photoelectron spectroscopy (XPS), which also give information on interfacial properties. The order in the SAM and orientation of molecules can be probed by Near Edge Xray Absorption Fine Structure (NEXAFS) and Fourier Transform Infrared Spectroscopy in Reflection Absorption Infrared Spectroscopy (RAIRS) studies. Numerous other spectroscopic techniques are used such as Second-harmonic generation (SHG), Sum-frequency generation (SFG), Surface-enhanced Raman scattering (SERS), as well as High-resolution electron energy loss spectroscopy (HREELS).  The structures of SAMs are commonly determined using scanning probe microscopy techniques such as atomic force microscopy (AFM) and scanning tunneling microscopy (STM). STM has been able to help understand the mechanisms of SAM formation as well as determine the important structural features that lend SAMs their integrity as surface-stable entities. In particular STM can image the shape, spatial distribution, terminal groups and their packing structure. AFM offers an equally powerful tool without the requirement of the SAM being conducting or semi-conducting. AFM has been used to determine chemical functionality, conductance, magnetic properties, surface charge, and frictional forces of SAMs. The scanning vibrating electrode technique (SVET) is a further scanning probe microscopy which has been used to characterize SAMs, with defect free SAMs showing homogeneous activity in SVET. More recently, however, diffractive methods have also been used. The structure can be used to characterize the kinetics and defects found on the monolayer surface. These techniques have also shown physical differences between SAMs with planar substrates and nanoparticle substrates.
An alternative characterisation instrument for measuring the self-assembly in real time is dual polarisation interferometry where the refractive index, thickness, mass and birefringence of the self assembled layer are quantified at high resolution. Another method that can be used to measure the self-assembly in real-time is Quartz Crystal Microbalance with Dissipation monitoring technology where the mass and viscoelastic properties of the adlayer are quantified. Contact angle measurements can be used to determine the surface free-energy which reflects the average composition of the surface of the SAM and can be used to probe the kinetics and thermodynamics of the formation of SAMs. The kinetics of adsorption and temperature induced desorption as well as information on structure can also be obtained in real time by ion scattering techniques such as low energy ion scattering (LEIS) and time of flight direct recoil spectroscopy (TOFDRS).