With the constant increasing demand for faster and more efficient electronic devices, the requirement for smaller integrated circuits has grown exponentially. The current method of fabrication for these devices, known as photolithography, employs a ‘top-down’ approach using light and masks for the patterning of substrate surfaces. This method, however, is reaching its size limits and has become extremely costly to carry out. Research into the fabrication of polymer brushes for the use in area selective deposition is vital for the understanding of ‘bottom up’ lithography techniques, such as block copolymer lithography. Such methods rely on the self-assembly of polymers containing active and inactive regions and are being proposed as an alternative to the current ‘top-down’ methods used for the manufacturing of electronic devices. These self-assembled polymer patterns can be exposed to infiltrating materials via a vapour phase process thus allowing for the infiltration of the active regions while blocking deposition in the inactive areas. A major part of these fields is investigating the polymer materials that will either accept or block infiltration by different species such as metals. This work looks at developing fabrication techniques of polymer brushes with a focus on increasing the overall thickness. It then goes on to investigate the infiltration of different polymers as well as looking at the effect that thickness has on a polymers infiltration and blocking mechanisms using hard X-Ray photoelectron spectroscopy as the core analysis method alongside techniques such as ellipsometry, atomic force microscopy and X-Ray reflectivity.