TEMPO growth was investigated using SiO2, HOPG, and Au(111) as substrate materials. SiO2 substrates are frequently used to characterise plasma polymerisation deposition and are therefore used as a reference substrate. In comparison, Au(111) and HOPG are wellstudied atomically flat materials known to promote good ordering in monolayer molecular films . Furthermore, whilst both are atomically flat, the chemical activity of Au(111) and HOPG are different; a property that is frequently exploited for molecular self-assembly on Au(111) . This combination of properties therefore allows us to gain insight into the effect of surface topography and chemical reactivity on the early stages of plasma polymerisation, and the potential to grow ordered monolayer films.