Scanning Near-Field Optical Lithography and Microscopy of Conjugated Polymer Structures

This thesis is concerned with the use of the scanning near-field optical microscope (SNOM) to pattern and image conjugated polymer structures. The SNOM is one of just a few optical instruments which are capable of breaking the diffraction limit which limits conventional microscopes to a resolution of approximately half a wavelength. It does so by directing light onto a sub-wavelength aperture at the apex of a probe, establishing a local evanescent field of subwavelength dimensions around the aperture. Conjugated polymers on the other hand are an interesting class of materials which have semiconducting properties and a rich photophysics making them suitable for use in novel light-emitting diodes, transistors and solar cells. I demonstrate direct patterning of several conjugated polymers using the SNOM with a resolution extending below 100 nm and attempt to explain the resolution of the lithography through simulations using the Bethe-Bouwkamp model o f the field surrounding a sub-wavelength aperture. In particular the modelling focuses on the role of the film thickness and reflections from the substrate. Further experiments demonstrate that thermal effects which can be caused by heating of the SNOM probe do not play a role in lithography with the SNOM in this case. However, I demonstrate the use of a scanning thermal microscope to do a novel and purely thermal lithography on one of the same conjugated polymers. Resolutions of 120 nm are demonstrated, and finite element analysis is used to show that significant improvements in resolution should be possible by optimisation of the probe and the polymer film. In addition, I present simulations of imaging artefacts caused by topography on samples under SNOM investigation, and use the same model to look at the potential of the SNOM to obtain information about sub-surface objects. SNOM images are presented of blends and supramolecular fibres of conjugated polymers.