In general, for SAMs of short hydrocarbon molecules, the molecular orientation is associated with SAM’s thickness. You can measure the thickness with Atomic Force Microscopy (AFM)-based techniques. For instance, you can locally “nanoshave” a SAM by scanning with an AFM tip in contact mode at a high force (ca. 100 nN) in a liquid cell in the presence of an appropriate solvent. Alternatively, you can “nanograft” a patch of a reference SAM of a SAM-forming molecule that is added in solution during the abovementioned process. Then you measure the topographic height change across the pit / patch with respect to the surrounding SAM. In the case you “nanoshave”, the height change that you measure equals SAM thickness. In the case you “nanograft”, the relative height change that you measure equals the difference between the thickness of the SAM and that of the patch The thickness of a SAM/patch always depends on the force applied during the topographic imaging. So I suggest you use 1nN or less for accurate measurements.
Technique is available with Atomic Force Microscope (AFM) and Scanning Electron Microscope (SEM) to measure tilting direction. Overall SEM is better than AFM. You go to an SEM or AFM operator and tell your problem.
As suggested you can use AFM, but you can also try by means of X-ray photoelectron spectroscopy (XPS). With this analysis you can have complementary information about your SAM, in association with AFM data. There are many example in litereature, but usually this kind of analysis require some skills....If you need I can give you some references.