The field of nanoscience is a rapidly expanding area of research with numerous applications for technology. The development of this field has been largely helped by the invention of the atomic force microscope, as well as other surface analytical techniques such as photoelectron spectroscopy. The studies described in this thesis cover a varied range of topics. These include polymeric systems, carbon nanotube and an organostannoxane cluster system. The common theme within these studies is in improving understanding of the fundamental processes that may occur in the self assembly of these systems on substrates. Chapter 1 is an introductory chapter in that the basic concepts regarding the field of nanotechnology are introduced. In Chapter 2 the important analytical probes used in this thesis are described i.e. atomic force microscopy and photoelectron spectroscopy. The ‘parent’ complex of the systems explored in Chapter 3 and Chapter 4, [Ru(bpy)3]2+, is introduced in Chapter 3. This is followed by an exploration of the self-assembly and the morphology observed for the redox polymer [Ru(bpy)2PVPioCl]Cl on a Si02/Si(l 11) substrate. The electronic structure of this polymer is also described using synchrotron radiation photoemission. Chapter 4 describes the modification of multi-wall carbon nanotubes with the inorganic ruthenium complex [&zs-(2,2 ’-bipyridine)-(4,4’-dicarboxy-2,2’-bipyridine) ruthenium (II)]. The resulting assembly is characterised using spectroscopic and atomic force microscopy techniques. An introduction to carbon nanotubes with a discussion on some of their potential applications is also given. In Chapter 5 atomic force microscopy imaging with subsequent statistical crystallographic analysis is used to investigate the morphology observed when an organostannoxane cluster is deposited onto a Si02/Si(lll) substrate. Advanced image analysis techniques based on Minkowski functionals is also used to provide a detailed quantitative analysis of the morphology of the organostannoxane overlayers. Variations in both the surface roughness and the in-plane correlation length are followed as a function of annealing time in order to probe the surface dewetting dynamics. The solid state electronic structure of the cluster is described using synchrotron radiation photoemission and resonant photoemission. Finally, in Chapter 6 the results of the work undertaken are summarised with suggestions on further possible research directions.